Functionalization of organic molecules using metal-organic frameworks (MOFS) as catalysts

ABSTRACT

The disclosure provides for catalytic multivariate metal organic frameworks and methods of use thereof.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a U.S. National Stage Application filed under 35U.S.C. §371 and claims priority to International Application No.PCT/US2011/044625, filed Jul. 20, 2011, which application claimspriority under 35 U.S.C. §119 from Provisional Application Ser. No.61/365,901, filed Jul. 20, 2010, the disclosures of which areincorporated herein by reference in their entirety.

TECHNICAL FIELD

The disclosure provides organic frameworks for catalyzing thefunctionalization of organic molecules.

BACKGROUND

The oxidization of alkanes has the important practical implication ofproviding valuable intermediates for chemical synthesis. Nevertheless,selective oxyfunctionalization of hydrocarbons remains one of the greatchallenges for contemporary chemistry. Many chemical methods foroxidizing alkanes require severe conditions of temperature or pressure,and the reactions are prone to over-oxidation, producing a range ofproducts, many of which are not desired. In addition, other methods tofunctionalize hydrocarbons, require using environmentally harmfulagents, such as halide gases.

SUMMARY

The disclosure provides a method to replace at least one atom of anorganic molecule with another atom or group of atoms by contacting itwith a metal organic framework. In one embodiment, the organic moleculeis a hydrocarbon. In another embodiment, a hydrogen of the organicmolecule is replaced with an oxygen containing functional group. Inanother embodiment, the method is carried out in the presence of CO. Inyet another embodiment, the method is carried out in the presence of anoxidant. In yet another embodiment, the organic molecule is an alkanethat is converted to a carboxylic acid. In one embodiment, the metalorganic framework comprises a metal or a metal ion comprising an alkalimetal, alkaline earth metal, transition metal, lanthanoid, actinoid,metalloid, or post transition metal. In any of the foregoingembodiments, the metal organic framework comprises a metal or a metalion selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺,Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Sc²⁺, Sc⁺, Y³⁺, Y²⁺, Y⁺, Ti⁴⁺, Ti³⁺, Ti²⁺,Zr⁴⁺, Zr³⁺, Zr²⁺, Hf⁴⁻, Hf³⁻, V⁵⁺, V⁴⁻, V³⁺, V²⁺, Nb⁵⁺, Nb⁴⁺, Nb³⁺,Nb²⁺, Ta⁵⁺, Ta⁴⁺, Ta³⁺, Ta²⁺, Cr⁶⁺, Cr⁵⁺, Cr⁴⁺, Cr³⁺, Cr²⁺, Cr⁺, Cr,Mo⁶⁺, Mo⁵⁺, Mo⁴⁺, Mo³⁺, Mo²⁺, Mo⁺, Mo, W⁶⁺, W⁵⁺, W⁴⁺, W³⁺, W²⁺, W⁺, W,Mn⁷⁺, Mn⁶⁺, Mn⁵⁺, Mn⁴⁺, Mn³⁺, Mn²⁻, Mn⁺, Re⁷⁺, Re⁶⁺, Re⁵⁺, Re⁴⁺, Re³⁺,Re²⁺, Re⁺, Re, Fe⁶⁺, Fe⁴⁺, Fe³⁺, Fe²⁺, Fe⁺, Fe, Ru⁸⁺, Ru⁷⁺, Ru⁶⁺, Ru⁴⁺,Ru³⁺, R²⁺, Os⁸⁺, Os⁷⁺, Os⁶⁺, Os⁵⁺, Os⁴⁺, Os³⁺, Os²⁺, Os⁺, Os, Co⁵⁺,Co⁴⁻, Co³⁺, Co²⁺, Co⁺, Rh⁶⁺, Rh⁵⁺, Rh⁴⁺, Rh³⁺, Rh²⁺, Rh⁺, Ir⁶⁺, Ir⁵⁺,Ir⁴⁺, Ir³⁺, Ir²⁺, Ir⁺, Ir, Ni³⁺, Ni²⁻, Ni⁺, Ni, Pd⁶⁺, Pd⁴⁺, Pd²⁺, Pd⁺,Pd, Pt⁶⁺, Pt⁵⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Pt⁺, Cu⁴⁺, Cu³⁺, C²⁺, Cu⁺, Ag³⁺, Ag²⁺,Ag⁺, Au⁵⁻, Au⁴⁺, Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn, Zn, Cd²⁺, Cd⁺, Hg⁴⁺, Hg²⁺,Hg⁺, B³⁺, B²⁺, B⁺, Al³⁺, Al²⁺, Al⁺, Ga³⁺, Ga²⁺, Ga⁺, In³⁺, In²⁺, In¹⁺,Tl³⁺, Tl⁺, Si⁴⁻, Si³⁺, Si²⁺, Si⁺, Ge⁴⁺, Ge³⁺, Ge²⁺, Ge⁺, Ge, Sn⁴⁺, Sn²⁺,Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As²⁺, As⁺, Sb⁵⁺, Sb³⁺, Bi⁵⁺, Bi³⁺, Te⁶⁺, Te⁵⁺,Te⁴⁺, Te²⁺, La³⁺, La²⁺, Ce⁴⁺, Ce³⁺, Ce²⁺, Pr⁴⁺, Pr³⁺, Pr²⁺, Nd³⁺, Nd²⁺,Sm³⁺, Sm²⁺, Eu³⁺, Eu²⁺, Gd³⁺, Gd²⁺, Gd⁺, Tb⁴⁻, Tb³⁺, Tb²⁺, Tb⁺, Db³⁺,Db²⁺, Ho³⁺, Er³⁺, Tm⁴⁺, Tm³⁺, Tm²⁺, Yb³⁻, Yb²⁺, and Lu³. In anotherembodiment, the metal organic framework has a metal or metal ion with amolecular geometry selected from the group consisting of trigonalplanar, tetrahedral, square planar, trigonal bipyramidal, squarepyramidal, octahedral, trigonal prismatic, pentagonal bipyramidal,paddle-wheel, and square antiprismatic. In yet another embodiment of anyof the foregoin the metal organic framework has one or more metals ormetal ions with a coordination number selected from the group consistingof 2, 4, 6, and 8. In yet another embodiment, the metal organicframework comprises a plurality of metals or metal ions selected fromthe group consisting of alkali metal, alkaline earth metal, transitionmetal, lanthanoid, actinoid, metalloid, and post transition metal. Inanother embodiment, the metal organic framework has a linking moietywith a parent chain selected from the group consisting of hydrocarbon,hetero-alkane, hetero-alkene, hetero-alkyne, and heterocycle; andwherein the parent chain is functionalized with at least one linkingcluster. In another embodiment, the metal organic framework is generatedfrom a linking moiety comprising structural Formula I, II, III, IV, V,VI, VII, VIII, IX and X:

wherein:

R¹-R⁴, R¹⁵-R²⁰, R²³-R³⁰, R³⁸-R⁹⁶ are independently selected from thegroup comprising H, FG, (C₁-C₂₀)alkyl, substituted (C₁-C₂₀)alkyl,(C₁-C₂₀)alkenyl, substituted (C₁-C₂₀)alkenyl, (C₁-C₂₀)alkynyl,substituted (C₁-C₂₀)alkynyl, hetero-(C₁-C₂₀)alkyl, substitutedhetero-(C₁-C₂₀)alkyl, hetero-(C₁-C₂₀)alkenyl, substitutedhetero-(C₁-C₂₀)alkenyl, hetero-(C₁-C₂₀)alkynyl, substitutedhetero-(C₁-C₂₀)alkynyl, (C₁-C₂₀)cycloalkyl, substituted(C₁-C₂₀)cycloalkyl, aryl, substituted aryl, heterocycle, substitutedheterocycle, —C(R⁵)₃, —CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶,—OC(R⁵)₃, —OCH(R⁵)₂, —OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

wherein R¹ and R³ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle, wherein R² and R⁴ are linked together to form asubstituted or unsubstituted ring selected from the group comprisingcycloalkyl, aryl and heterocycle, wherein R¹⁸ and R¹⁹ are linkedtogether to form a substituted or unsubstituted ring selected from thegroup comprising cycloalkyl, aryl and heterocycle, wherein R²⁴ and R²⁵are linked together to form a substituted or unsubstituted ring selectedfrom the group comprising cycloalkyl, aryl and heterocycle, and/orwherein R²⁸ and R²⁹ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle;

R⁵ is selected from the group comprising FG, (C₁-C₂₀)alkyl,(C₁-C₂₀)substituted alkyl, (C₁-C₂₀)alkenyl, substituted (C₁-C₂₀)alkenyl,(C₁-C₂₀)alkynyl, substituted (C₁-C₂₀)alkynyl, hetero-(C₁-C₂₀)alkyl,substituted hetero-(C₁-C₂₀)alkyl, hetero-(C₁-C₂₀)alkenyl, substitutedhetero-(C₁-C₂₀)alkenyl, hetero-(C₁-C₂₀)alkynyl, substitutedhetero-(C₁-C₂₀)alkynyl, hemiacetal, hemiketal, acetal, ketal, and/ororthoester;

R₆ is one or more substituted or unsubstituted rings selected from thegroup comprising cycloalkyl, aryl, and/or heterocycle; and

X is a number from 0 to 10.

In one embodiment, the metal organic framework is generated from aplurality of linking moieties comprising structural Formula I, II, III,IV, V, VI, VII, VIII, IX and X:

wherein:

R¹-R⁴, R¹⁵-R²⁰, R²³-R³⁰, R³⁸-R⁹⁶ are independently selected from thegroup comprising H, FG, (C₁-C₂₀)alkyl, substituted (C₁-C₂₀)alkyl,(C₁-C₂₀)alkenyl, substituted (C₁-C₂₀)alkenyl, (C₁-C₂₀)alkynyl,substituted (C₁-C₂₀)alkynyl, hetero-(C₁-C₂₀)alkyl, substitutedhetero-(C₁-C₂₀)alkyl, hetero-(C₁-C₂₀)alkenyl, substitutedhetero-(C₁-C₂₀)alkenyl, hetero-(C₁-C₂₀)alkynyl, substitutedhetero-(C₁-C₂₀)alkynyl, (C₁-C₂₀)cycloalkyl, substituted(C₁-C₂₀)cycloalkyl, aryl, substituted aryl, heterocycle, substitutedheterocycle, —C(R⁵)₃, —CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶,—OC(R⁵)₃, —OCH(R⁵)₂, —OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

wherein R¹ and R³ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle, wherein R² and R⁴ are linked together to form asubstituted or unsubstituted ring selected from the group comprisingcycloalkyl, aryl and heterocycle, wherein R¹⁸ and R¹⁹ are linkedtogether to form a substituted or unsubstituted ring selected from thegroup comprising cycloalkyl, aryl and heterocycle, wherein R²⁴ and R²⁵are linked together to form a substituted or unsubstituted ring selectedfrom the group comprising cycloalkyl, aryl and heterocycle, and/orwherein R²⁸ and R²⁹ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle;

R⁵ is selected from the group comprising FG, (C₁-C₂₀)alkyl,(C₁-C₂₀)substituted alkyl, (C₁-C₂₀)alkenyl, substituted (C₁-C₂₀)alkenyl,(C₁-C₂₀)alkynyl, substituted (C₁-C₂₀)alkynyl, hetero-(C₁-C₂₀)alkyl,substituted hetero-(C₁-C₂₀)alkyl, hetero-(C₁-C₂₀)alkenyl, substitutedhetero-(C₁-C₂₀)alkenyl, hetero-(C₁-C₂₀)alkynyl, substitutedhetero-(C₁-C₂₀)alkynyl, hemiacetal, hemiketal, acetal, ketal, and/ororthoester;

R₆ is one or more substituted or unsubstituted rings selected from thegroup comprising cycloalkyl, aryl, and/or heterocycle; and

X is a number from 0 to 10.

In another embodiment, the metal organic framework is generated from alinking moiety comprising structural Formula I, II, III, IV, V, VI, VII,and VIII:

wherein:

R¹-R⁴, R¹⁵-R²⁰, R²³-R³⁰, R³⁸-R⁸⁸ are independently selected from thegroup comprising H, FG, (C₁-C₆)alkyl, substituted (C₁-C₆)alkyl,(C₁-C₆)alkenyl, substituted (C₁-C₆)alkenyl, (C₁-C₆)alkynyl, substituted(C₁-C₆)alkynyl, hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₁-C₆)alkenyl,hetero-(C₁-C₆)alkynyl, substituted hetero-(C₁-C₆)alkynyl,(C₁-C₆)cycloalkyl, substituted (C₁-C₆)cycloalkyl, aryl, substitutedaryl, heterocycle, substituted heterocycle, —C(R⁵)₃, —CH(R⁵)₂, —CH₂R⁵,—C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂, —OCH₂R⁵, —OC(R⁶)₃,—OCH(R⁶)₂, —OCH₂R⁶,

wherein R¹ and R³ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle, wherein R² and R⁴ are linked together to form asubstituted or unsubstituted ring selected from the group comprisingcycloalkyl, aryl and heterocycle, wherein R¹⁸ and R¹⁹ are linkedtogether to form a substituted or unsubstituted ring selected from thegroup comprising cycloalkyl, aryl and heterocycle, wherein R²⁴ and R²⁵are linked together to form a substituted or unsubstituted ring selectedfrom the group comprising cycloalkyl, aryl and heterocycle, and/orwherein R²⁸ and R²⁹ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle;

R⁵ is selected from the group comprising FG, (C₁-C₆)alkyl,(C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl, substituted (C₁-C₆)alkenyl,(C₁-C₆)alkynyl, substituted (C₁-C₆)alkynyl, hetero-(C₁-C₆)alkyl,substituted hetero-(C₁-C₆)alkyl, hetero-(C₁-C₆)alkenyl, substitutedhetero-(C₁-C₆)alkenyl, hetero-(C₁-C₆)alkynyl, substitutedhetero-(C₁-C₆)alkynyl, hemiacetal, hemiketal, acetal, ketal, and/ororthoester;

R₆ is one or more substituted or unsubstituted rings selected from thegroup comprising cycloalkyl, aryl, and/or heterocycle; and

X is a number from 0 to 3.

In yet another embodiment, the metal organic framework is generated froma plurality of linking moieties comprising structural Formula I, II,III, IV, V, VI, VII, and VIII:

wherein:

R¹-R⁴, R¹⁵-R²⁰, R²³-R³⁰, R³⁸-R⁸⁸ are independently selected from thegroup comprising H, FG, (C₁-C₆)alkyl, substituted (C₁-C₆)alkyl,(C₁-C₆)alkenyl, substituted (C₁-C₆)alkenyl, (C₁-C₆)alkynyl, substituted(C₁-C₆)alkynyl, hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₁-C₆)alkenyl,hetero-(C₁-C₆)alkynyl, substituted hetero-(C₁-C₆)alkynyl,(C₁-C₆)cycloalkyl, substituted (C₁-C₆)cycloalkyl, aryl, substitutedaryl, heterocycle, substituted heterocycle, —C(R⁵)₃, —CH(R⁵)₂, —CH₂R⁵,—C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂, —OCH₂R⁵, —OC(R⁶)₃,—OCH(R⁶)₂, —OCH₂R⁶,

wherein R¹ and R³ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle, wherein R² and R⁴ are linked together to form asubstituted or unsubstituted ring selected from the group comprisingcycloalkyl, aryl and heterocycle, wherein R¹⁸ and R¹⁹ are linkedtogether to form a substituted or unsubstituted ring selected from thegroup comprising cycloalkyl, aryl and heterocycle, wherein R²⁴ and R²⁵are linked together to form a substituted or unsubstituted ring selectedfrom the group comprising cycloalkyl, aryl and heterocycle, and/orwherein R²⁸ and R²⁹ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle;

R⁵ is selected from the group comprising FG, (C₁-C₆)alkyl,(C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl, substituted (C₁-C₆)alkenyl,(C₁-C₆)alkynyl, substituted (C₁-C₆)alkynyl, hetero-(C₁-C₆)alkyl,substituted hetero-(C₁-C₆)alkyl, hetero-(C₁-C₆)alkenyl, substitutedhetero-(C₁-C₆)alkenyl, hetero-(C₁-C₆)alkynyl, substitutedhetero-(C₁-C₆)alkynyl, hemiacetal, hemiketal, acetal, ketal, and/ororthoester;

R₆ is one or more substituted or unsubstituted rings selected from thegroup comprising cycloalkyl, aryl, and/or heterocycle; and X is a numberfrom 0 to 3. In another embodiment, the metal organic framework isgenerated from a linking moiety comprising structural Formula I:

wherein:

R¹-R⁴ are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶.

wherein R¹ and R³ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle, and/or wherein R² and R⁴ are linked together to form asubstituted or unsubstituted ring selected from the group comprisingcycloalkyl, aryl and heterocycle;

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and/or orthoester;

R₆ is one or more substituted or unsubstituted rings selected from thegroup comprising cycloalkyl, aryl, and/or heterocycle; and

X is a number from 0 to 3.

In another embodiment, the linking moiety is generated from the groupconsisting of

In another embodiment, at least one of the functional groups of themetal organic framework is further modified, substituted, or eliminatedwith a different functional group post-synthesis of the framework. Inone embodiment, the metal organic framework is further modified byadding a functional group post synthesis of the framework that has oneor more properties selected from the group consisting of: binds a metalion, increases the hydrophobicity of the framework, modifies the gassorption of the framework, modifies the pore size of the framework, andtethers a catalyst to the framework. In yet another embodiment, themetal organic framework is a composition comprising a vanadiumcontaining metal organic framework.

This disclosure describes a heterogeneous and efficient route tofunctionalize various types of organic molecules by replacing an atomfrom an organic molecule with another atom or a group of atoms. It wassurprisingly found that metal organic frameworks (MOFs), e.g., vanadiumcontaining MOFs, and other MOFs catalyze the oxidation of various typesof alkanes, in the presence or absence of carbon monoxide, to formoxidized products, including alcohols, homologous carboxylic acids, andcarboxylic acids. In one embodiment, the reaction is carried out intrifluoroacetic acid (TFA), wherein the desired alcohol is trapped asthe corresponding TFA ester. Potasium persulfate (KPS) is used as anoxidant, although water and hydrogen peroxide can alternatively be usedas the solvent and oxidant, respectively. In one embodiment, thedisclosure provides a method to convert methane to acetic acid andethane to propanoic acid by contacting with a MOF disclosed herein.Further transformations, however, are possible by using the appropriatelinker molecule and/or appropriate post synthesized framework reactant.

MOF-V150 was obtained by reacting 2,5-dimethyl-benzen-dicarboxylic andvanadium (IV) oxide (VO₂) in hydrochloric acid and water at 220° C. for3 days.

The details of one or more embodiments of the invention are set forth inthe accompanying drawings and the description below. Other features,objects, and advantages of the invention will be apparent from thedescription and drawings, and from the claims.

DESCRIPTION OF DRAWINGS

FIG. 1 shows the coordination complex of MIL-47 and MOF-V150, whereineach V is coordinated by four μ²-carboxylate moieties and two μ²-oxogroups forming an octahedral coordination sphere.

FIG. 2A-D depicts structures of the disclosure. (A) Amavandin complexstructures are shown in a ball and stick presentation (V=larger lightgrey ball, O=light grey, N=dark grey balls connected to V, C=dark greyballs not connected to V). The inorganic SBUs of MOF-V150 and MIL-47 arechains of corner—sharing V octahedra (VO₆) that are shown in a ball andstick presentation (B) (V=larger ball light grey, O=light grey balls,N=dark grey balls connected to V, C=dark grey balls not connected to V).(C) The VO₆ of SBUs is shown in blue polyhedra. (D) Extended networks ofMOF-150 (top) and MIL-47 (bottom). H atoms are omitted for clarity.

FIG. 3 shows ¹³C NMR of the reaction mixture of ¹³CH₄ in the absence ofCO.

FIG. 4 shows ¹³C NMR of the reaction mixture of ¹³CH₄ in the presence ofCO.

FIG. 5A-B shows catalytic activity of (a) MOF-V150 and (b) MIL-47 in thedirect conversion of methane to acetic acid over four recycling steps.

FIG. 6 shows PXRD patterns of MOF-150 before (black) and after (blue)the catalytic reaction.

DETAILED DESCRIPTION

As used herein and in the appended claims, the singular forms “a,”“and,” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “a framework”includes a plurality of such frameworks and reference to “the metal”includes reference to one or more metals and equivalents thereof knownto those skilled in the art, and so forth.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood to one of ordinary skill inthe art to which this disclosure belongs. Although many methods andreagents similar or equivalent to those described herein can be used inthe practice of the disclosed methods and compositions, the exemplarymethods and materials are disclosed herein.

Also, the use of “and” means “and/or” unless stated otherwise.Similarly, “comprise,” “comprises,” “comprising” “include,” “includes,”and “including” are interchangeable and not intended to be limiting.

It is to be further understood that where descriptions of variousembodiments use the term “comprising,” those skilled in the art wouldunderstand that in some specific instances, an embodiment can bealternatively described using language “consisting essentially of” or“consisting of.”

All publications mentioned herein are incorporated herein by referencein full for the purpose of describing and disclosing the methodologies,which are described in the publications, which might be used inconnection with the description herein. The publications discussed aboveand throughout the text are provided solely for their disclosure priorto the filing date of the present application. Nothing herein is to beconstrued as an admission that the inventors are not entitled toantedate such disclosure by virtue of prior disclosure. Moreover, withrespect to similar or identical terms found in the incorporatedreferences and terms expressly defined in this disclosure, the termdefinitions provided in this disclosure will control in all respects.

A “metal” refers to a solid material that is typically hard, shiny,malleable, fusible, and ductile, with good electrical and thermalconductivity. “Metals” used herein refer to metals selected from alkalimetals, alkaline earth metals, lanthanides, actinides, transitionmetals, and post transition metals.

A “metal ion” refers to an ion of metal. Metal ions are generally LewisAcids and can form coordination complexes. Typically, the metal ionsused for forming a coordination complex in a framework are ions oftransition metals.

A “ligand” refers to an atom, or a group of atoms, that have denticityand are therefore able to form at least one bond with at least one metalor metal ion from a parental chain (e.g., a linking moietysubstructure).

The term “cluster” refers to identifiable associations of 2 or moreatoms. Such associations are typically established by some type ofbond-ionic, covalent, Van der Waal, coordinate and the like. A clustercan be a ligand, except when the cluster is a linking cluster.

The term “linking cluster” refers to one or more reactive speciescapable of condensation comprising an atom capable of forming a bondbetween a linking moiety parent chain (e.g., substructure) and a metalgroup or between a linking moiety and another linking moiety. A linkingcluster would include a coordination complex defined herein. A linkingcluster can be part of the parent chain itself, e.g. imidiazoles, oralternatively can arise from functionalizing the parent chain, e.g.adding carboxylic acid groups to aryls. Examples of such reactivespecies include, but is not limited to, boron, oxygen, carbon, nitrogen,silicon, tin, germanium, arsenic, and phosphorous. In certainembodiments, the linking cluster may comprise one or more differentreactive species capable of forming a link with a bridging oxygen atom.For example, a linking cluster can comprise CO₂H, CS₂H, NO₂, SO₃H,Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H,AsO₄H, P(SH)₃, As(SH)₃, CH(RSH)₂, C(RSH)₃, CH(RNH₂)₂, C(RNH₂)₃,CH(ROH)₂, C(ROH)₃, CH(RCN)₂, C(RCN)₃, CH(SH)₂, C(SH)₃, CH(NH₂)₂,C(NH₂)₃, CH(OH)₂, C(OH)₃, CH(CN)₂, and C(CN)₃, wherein R is an alkylgroup having from 1 to 5 carbon atoms, or an aryl group comprising 1 to2 phenyl rings and CH(SH)₂, C(SH)₃, CH(NH₂)₂, C(NH₂)₃, CH(OH)₂, C(OH)₃,CH(CN)₂, and C(CN)₃. Typically linking clusters for binding metals inthe generation of MOFs contain carboxylic acid functional groups.Linking clusters are generally Lewis bases, and therefore have lone pairelectrons available and/or can be deprotonated to form stronger Lewisbases. The deprotonated version of the linking clusters, therefore, isencompassed by invention and anywhere a linking cluster that is depictedin a nondeprotenated form, the deprotenated form should be presumed tobe included, unless stated otherwise. For example, although thestructural Formulas presented herein are illustrated as havingcarboxylic acid ligands, for the purposes of this invention, theseillustrated structures should be interpreted as including bothcarboxylic acid and/or carboxylate ligands.

The term “coordination number” refers to the number of atoms, groups ofatoms, or linking clusters that bind to a central metal or metal ionwhere only the sigma bond between each atom, groups of atoms, or linkingcluster and the central atom counts.

The term “coordination complex” refers to a metal or a metal ion that iscoordinated by one or more linking clusters and/or ligands of one ormore linking moieties and/or ions by forming coordinate bonds with acentral metal or metal ion. For purposes of this invention a“coordination complex” includes complexes arising from linking moietiesthat have mono-dentate and/or polydentate ligands.

The term “denticity” or “dentate” with respect to mono-dentate orpolydentate, refers to the number of atoms of a ligand, which can form abond to a metal and/or metal ion in a coordination complex. Examples ofpolydentate functional groups, include, but are not limited to,carboxylic acids, diamines, diimines, dithiolates, diketonates,bipyrimidinyls, diphosphinos, oxalates, tri-aza-based compounds, andtetra-aza-based compounds. It is understood that ligands possessingmonodentate and/or polydentate functional groups bring with themcorresponding counter cations, such as H⁺, Na⁺, K⁺, Mg²⁻, Ca²⁺, Sr²⁺,ammonium ions, alkyl substituted ammonium ions, and aryl substitutedammonium ions; or with corresponding counter anions, such as F⁻, Cl⁻,Br⁻, I⁻, ClO⁻, ClO₂ ⁻, ClO₃ ⁻, ClO₄ ⁻, OH⁻, NO₃ ⁻, NO₂ ⁻, SO₄ ⁻, SO₃ ⁻,PO₃ ⁻, CO₃ ⁻, PF₆ ⁻, and organic counter ions such as acetate CH₃CO₂ ⁻,triflates CF₃SO₃—, mesylates CH₃SO₃ ⁻, tosylates CH₃C₆H₄SO₃, and thelike.

A “linking moiety” refers to an organic compound which can form acoordination complex with one or more metal and/or metal ions.Generally, a linking moiety comprises a parent chain of a hydrocarbon,hetero-alkane, hetero-alkene, hetero-alkyne, or heterocycles; where thisparent chain may be substituted with one or more functional groups,including additional substituted or unsubstituted hydrocarbons, andheterocycles, or a combination thereof; and wherein the linking moietycontains at least one linking cluster. In the case of heterocycles,hetero-alkanes, hetero-alkenes, and hetero-alkynes, one or moreheteroatoms can function as linking clusters or alternatively asligands. Examples of such heteroatoms include, but are not limited to,nitrogen, oxygen, sulfur, boron, phosphorus, silicon or aluminum atomsmaking up the ring. Moreover, a heterocycle, hetero-alkane,hetero-alkene, or hetero-alkyne, can also be functionalized with one ormore linking clusters. Moreover, a heterocycle, hetero-alkane,hetero-alkene, or hetero-alkyne, can also be functionalized with one ormore ligands to add or increase denticity of the hetero-based parentchain. In the case of hydrocarbons, typically one or more of the linkingclusters of the hydrocarbon-based linking moiety can arise fromfunctionalizing the hydrocarbon parent chain with one or more functionalgroups that can then act as a linking cluster. Examples of such groups,include, but are not limited to, carboxylic acids, hydroxyls, amines,imines, thiols, phosphines, ketones, aldehydes, halides, cyanos, andnitros. In certain cases, portions of a hydrocarbon itself can functionas ligand, for example by forming carbenes and carbocations. It is alsowell known that functional groups that can be ligands are generallyLewis bases, and therefore have lone pair electrons available and/or canbe deprotonated to form stronger Lewis bases. The deprotonated versionof the ligand, therefore, is encompassed by invention and anywhere aligand that is depicted in a nondeprotenated form, the deprotenated formshould be presumed to be included, unless stated otherwise. For example,although the structural Formulas presented herein are illustrated ashaving carboxylic acid ligands, for the purposes of this invention,those illustrated structures should be interpreted as including bothcarboxylic acid and/or carboxylate ligands.

The term “alkyl” refers to an alkyl group that contains 1 to 30 carbonatoms. Where if there is more than 1 carbon, the carbons may beconnected in a linear manner, or alternatively if there are more than 2carbons then the carbons may also be linked in a branched fashion sothat the parent chain contains one or more secondary, tertiary, orquaternary carbons. An alkyl may be substituted or unsubstituted, unlessstated otherwise.

The term “alkenyl” refers to an alkenyl group that contains 1 to 30carbon atoms. While a C₁₋alkenyl can form a double bond to a carbon of aparent chain, an alkenyl group of three or more carbons can contain morethan one double bond. It certain instances the alkenyl group will beconjugated, in other cases an alkenyl group will not be conjugated, andyet other cases the alkenyl group may have stretches of conjugation andstretches of nonconjugation. Additionally, if there is more than 1carbon, the carbons may be connected in a linear manner, oralternatively if there are more than 3 carbons then the carbons may alsobe linked in a branched fashion so that the parent chain contains one ormore secondary, tertiary, or quaternary carbons. An alkenyl may besubstituted or unsubstituted, unless stated otherwise.

The term “alkynyl” refers to an alkynyl group that contains 1 to 30carbon atoms. While a C₁₋alkynyl can form a triple bond to a carbon of aparent chain, an alkynyl group of three or more carbons can contain morethan one triple bond. Where if there is more than 1 carbon, the carbonsmay be connected in a linear manner, or alternatively if there are morethan 4 carbons then the carbons may also be linked in a branched fashionso that the parent chain contains one or more secondary, tertiary, orquaternary carbons. An alkynyl may be substituted or unsubstituted,unless stated otherwise.

The term “cylcloalkyl” refers to an alkyl that contains at least 3carbon atoms but no more than 12 carbon atoms connected so that it formsa ring. A “cycloalkyl” for the purposes of this invention encompass from1 to 7 cycloalkyl rings, wherein when the cycloalkyl is greater than 1ring, then the cycloalkyl rings are joined so that they are linked,fused, or a combination thereof. A cycloalkyl may be substituted orunsubstituted, or in the case of more than one cycloalkyl ring, one ormore rings may be unsubstitued, one or more rings may be substituted, ora combination thereof.

The term “aryl” refers to a conjugated planar ring system withdelocalized pi electron clouds that contain only carbon as ring atoms.An “aryl” for the purposes of this invention encompass from 1 to 7 arylrings wherein when the aryl is greater than 1 ring the aryl rings arejoined so that they are linked, fused, or a combination thereof. An arylmay be substituted or unsubstituted, or in the case of more than onearyl ring, one or more rings may be unsubstituted, one or more rings maybe substituted, or a combination thereof.

The term “heterocycle” refers to ring structures that contain at least 1noncarbon ring atom. A “heterocycle” for the purposes of this inventionencompass from 1 to 7 heterocycle rings wherein when the heterocycle isgreater than 1 ring the heterocycle rings are joined so that they arelinked, fused, or a combination thereof. A heterocycle may be aromaticor nonaromatic, or in the case of more than one heterocycle ring, one ormore rings may be nonaromatic, one or more rings may be aromatic, or acombination thereof. A heterocycle may be substituted or unsubstituted,or in the case of more than one heterocycle ring one or more rings maybe unsubstituted, one or more rings may be substituted, or a combinationthereof. Typically, the noncarbon ring atom is either N, O, S, Si, Al,B, or P. In case where there is more than one noncarbon ring atom, thesenoncarbon ring atoms can either be the same element, or combination ofdifferent elements, such as N and O. Examples of heterocycles include,but is not limited to: a monocyclic heterocycle such as, aziridine,oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, pyrroline,imidazolidine, pyrazolidine, pyrazoline, dioxolane, sulfolane2,3-dihydrofuran, 2,5-dihydrofuran tetrahydrofuran, thiophane,piperidine, 1,2,3,6-tetrahydro-pyridine, piperazine, morpholine,thiomorpholine, pyran, thiopyran, 2,3-dihydropyran, tetrahydropyran,1,4-dihydropyridine, 1,4-dioxane, 1,3-dioxane, dioxane, homopiperidine,2,3,4,7-tetrahydro-1H-azepine homopiperazine, 1,3-dioxepane,4,7-dihydro-1,3-dioxepin, and hexamethylene oxide; and polycyclicheterocycles such as, indole, indoline, isoindoline, quinoline,tetrahydroquinoline, isoquinoline, tetrahydroisoquinoline,1,4-benzodioxan, coumarin, dihydrocoumarin, benzofuran,2,3-dihydrobenzofuran, isobenzofuran, chromene, chroman, isochroman,xanthene, phenoxathiin, thianthrene, indolizine, isoindole, indazole,purine, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline,pteridine, phenanthridine, perimidine, phenanthroline, phenazine,phenothiazine, phenoxazine, 1,2-benzisoxazole, benzothiophene,benzoxazole, benzthiazole, benzimidazole, benztriazole, thioxanthine,carbazole, carboline, acridine, pyrolizidine, and quinolizidine. Inaddition to the polycyclic heterocycles described above, heterocycleincludes polycyclic heterocycles wherein the ring fusion between two ormore rings includes more than one bond common to both rings and morethan two atoms common to both rings. Examples of such bridgedheterocycles include quinuclidine, diazabicyclo[2.2.1]heptane and7-oxabicyclo[2.2.1]heptane.

The terms “heterocyclic group”, “heterocyclic moiety”, “heterocyclic”,or “heterocyclo” used alone or as a suffix or prefix, refers to aheterocycle that has had one or more hydrogens removed therefrom.

The term “heterocyclyl” used alone or as a suffix or prefix, refers amonovalent radical derived from a heterocycle by removing one hydrogentherefrom. Heterocyclyl includes, for example, monocyclic heterocyclyls,such as, aziridinyl, oxiranyl, thiiranyl, azetidinyl, oxetanyl,thietanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, pyrazolidinyl,pyrazolinyl, dioxolanyl, sulfolanyl, 2,3-dihydrofuranyl,2,5-dihydrofuranyl, tetrahydrofuranyl, thiophanyl, piperidinyl,1,2,3,6-tetrahydro-pyridinyl, piperazinyl, morpholinyl, thiomorpholinyl,pyranyl, thiopyranyl, 2,3-dihydropyranyl, tetrahydropyranyl,1,4-dihydropyridinyl, 1,4-dioxanyl, 1,3-dioxanyl, dioxanyl,homopiperidinyl, 2,3,4,7-tetrahydro-1H-azepinyl, homopiperazinyl,1,3-dioxepanyl, 4,7-dihydro-1,3-dioxepinyl, and hexamethylene oxidyl. Inaddition, heterocyclyl includes aromatic heterocyclyls or heteroaryl,for example, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl,furyl, furazanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, pyrazolyl,isothiazolyl, isoxazolyl, 1,2,3-triazolyl, tetrazolyl,1,2,3-thiadiazolyl, 1,2,3-oxadiazolyl, 1,2,4-triazolyl,1,2,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-triazolyl,1,3,4-thiadiazolyl, and 1,3,4 oxadiazolyl. Additionally, heterocyclylencompasses polycyclic heterocyclyls (including both aromatic ornon-aromatic), for example, indolyl, indolinyl, isoindolinyl,quinolinyl, tetrahydroquinolinyl, isoquinolinyl,tetrahydroisoquinolinyl, 1,4-benzodioxanyl, coumarinyl,dihydrocoumarinyl, benzofuranyl, 2,3-dihydrobenzofuranyl,isobenzofuranyl, chromenyl, chromanyl, isochromanyl, xanthenyl,phenoxathiinyl, thianthrenyl, indolizinyl, isoindolyl, indazolyl,purinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl,cinnolinyl, pteridinyl, phenanthridinyl, perimidinyl, phenanthrolinyl,phenazinyl, phenothiazinyl, phenoxazinyl, 1,2-benzisoxazolyl,benzothiophenyl, benzoxazolyl, benzthiazolyl, benzimidazolyl,benztriazolyl, thioxanthinyl, carbazolyl, carbolinyl, acridinyl,pyrolizidinyl, and quinolizidinyl. In addition to the polycyclicheterocyclyls described above, heterocyclyl includes polycyclicheterocyclyls wherein the ring fusion between two or more rings includesmore than one bond common to both rings and more than two atoms commonto both rings. Examples of such bridged heterocycles include, but is notlimited to, quinuclidinyl, diazabicyclo[2.2.1]heptyl; and7-oxabicyclo[2.2.1]heptyl.

The term “hetero-aryl” used alone or as a suffix or prefix, refers to aheterocyclyl having aromatic character. Examples of heteroaryls include,but is not limited to, pyridine, pyrazine, pyrimidine, pyridazine,thiophene, furan, furazan, pyrrole, imidazole, thiazole, oxazole,pyrazole, isothiazole, isoxazole, 1,2,3-triazole, tetrazole,1,2,3-thiadiazole, 1,2,3-oxadiazole, 1,2,4-triazole, 1,2,4-thiadiazole,1,2,4-oxadiazole, 1,3,4-triazole, 1,3,4-thiadiazole, and1,3,4-oxadiazole.

The term “hetero-” when used as a prefix, such as, hetero-alkyl,hetero-alkenyl, hetero-alkynyl, or hetero-hydrocarbon, for the purposeof this invention refers to the specified hydrocarbon having one or morecarbon atoms replaced by non carbon atoms as part of the parent chain.Examples of such noncarbon atoms include, but is not limited to, N, O,S, Si, Al, B, and P. If there is more than one noncarbon atom in thehetero-hydrocarbon chain then this atom may be the same element or maybe a combination of different elements, such as N and O.

The term “unsubstituted” with respect to hydrocarbons, heterocycles, andthe like, refers to structures wherein the parent chain contains nosubstituents.

The term “substituted” with respect to hydrocarbons, heterocycles, andthe like, refers to structures wherein the parent chain contains one ormore substituents.

The term “substituent” refers to an atom or group of atoms substitutedin place of a hydrogen atom. For purposes of this invention, asubstituent would include deuterium atoms.

The term “hydrocarbons” refers to groups of atoms that contain onlycarbon and hydrogen. Examples of hydrocarbons that can be used in thisinvention include, but is not limited to, alkanes, alkenes, alkynes,arenes, and benzyls.

The term “functional group” or “FG” refers to specific groups of atomswithin molecules that are responsible for the characteristic chemicalreactions of those molecules. While the same functional group willundergo the same or similar chemical reaction(s) regardless of the sizeof the molecule it is a part of, its relative reactivity can be modifiedby nearby functional groups. The atoms of functional groups are linkedto each other and to the rest of the molecule by covalent bonds.Examples of FG that can be used in this invention, include, but is notlimited to, substituted or unsubstituted alkyls, substituted orunsubstituted alkenyls, substituted or unsubstituted alkynyls,substituted or unsubstituted aryls, substituted or unsubstitutedhetero-alkyls, substituted or unsubstituted hetero-alkenyls, substitutedor unsubstituted hetero-alkynyls, substituted or unsubstitutedheteroaryls, substituted or unsubstituted heterocycles, halos,hydroxyls, anhydrides, carbonyls, carboxyls, carbonates, carboxylates,aldehydes, haloformyls, esters, hydroperoxy, peroxy, ethers,orthoesters, carboxamides, amines, imines, imides, azides, azos,cyanates, isocyanates, nitrates, nitriles, isonitriles, nitrosos,nitros, nitrosooxy, pyridyls, sulfhydryls, sulfides, disulfides,sulfinyls, sulfos, thiocyanates, isothiocyanates, carbonothioyls,phosphinos, phosphonos, phosphates, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄,Ge(SH)₄, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, AsO₃H, AsO₄H, P(SH)₃, and As(SH)₃.

As used herein, a “core” refers to a repeating unit or units found in aframework. Such a framework can comprise a homogenous repeating core, aheterogeneous repeating core or a combination of homogenous andheterogeneous cores. A core comprises a metal and/or metal ion or acluster of metal and/or metal ions and a linking moiety.

As used herein, a “framework” refers to crystalline structure consistingof plurality of cores to form one-, two-, or three-dimensionalstructures that may or may not be porous. In some cases, the pores arestable to elimination of the guest molecules (often solvents).

The term “covalent organic polyhedra” refers to a non-extended covalentorganic network. Polymerization in such polyhedra does not occur usuallybecause of the presence of capping ligands that inhibit polymerization.Covalent organic polyhedra are covalent organic networks that comprise aplurality of linking moieties linking together polydentate cores suchthat the spatial structure of the network is a polyhedron. Typically,the polyhedra of this variation are 2 or 3 dimensional structures.

The term “post framework reactants” refers to all known substances thatare directly involved in a chemical reaction. Post framework reactantstypically are substances, either elemental or compounds, which have notreached the optimum number of electrons in their outer valence levels,and/or have not reached the most favorable energetic state due to ringstrain, bond length, low bond dissociation energy, and the like. Someexamples of post framework reactants include, but are not limited to:

I—R, Br—R, CR₃—Mg—Br, CH₂R—Li, CR₃, Na—R, and K—R; and wherein each R isindependently selected from the group comprising: H, sulfonates,tosylates, azides, triflates, ylides, alkyl, aryl, OH, alkoxy, alkenes,alkynes, phenyl and substitutions of the foregoing, sulfur-containinggroups (e.g., thioalkoxy, thionyl chloride), silicon-containing groups,nitrogen-containing groups (e.g., amides and amines), oxygen-containinggroups (e.g., ketones, carbonates, aldehydes, esters, ethers, andanhydrides), halogen, nitro, nitrile, nitrate, nitroso, amino, cyano,ureas, boron-containing groups (e.g., sodium borohydride, andcatecholborane), phosphorus-containing groups (e.g., phosphoroustribromide), and aluminum-containing groups (e.g., lithium aluminumhydride).

As used herein, a wavy line intersecting another line that is connectedto an atom indicates that this atom is covalently bonded to anotherentity that is present but not being depicted in the structure. A wavyline that does not intersect a line but is connected to an atomindicates that this atom is interacting with another atom by a bond orsome other type of identifiable association.

A bond indicated by a straight line and a dashed line indicates a bondthat may be a single covalent bond or alternatively a double covalentbond. But in the case where an R group defines an atom that is connectedto another atom by a straight line and a dashed line which would exceedits maximum valence if the bond was a double covalent bond then the bondwould only be a single covalent bond. For example, where R can behydrogen and is connected to another atom by a straight line and adashed line, then hydrogen would only form a single bond even thoughsuch a bond is indicated as being a single or double bond.

Methane, the main component of natural gas, is an abundant, cleanburning, but relatively potent greenhouse gas. A long existingchallenge, due to the strong C—H bonds of methane (435 kJ mol⁻¹), is todirectly convert this inexpensive carbon source to other usefulmolecules. Many potential catalysts for the transformation of methane touseful raw materials for the chemical industry, including acetic acid(AcOH), have been investigated. Currently, the production of acetic acidon an industrial scale involves three steps: the partial-oxidation ofmethane to syn-gas using metal catalysts at high temperatures, followedby the conversion of the derived syn-gas to methanol, and finally, thecarbonylation of methanol to obtain acetic acid. These processes useexpensive catalyst systems containing either Rh or Ir compounds andrequire huge inputs of energy and capital.

Many efforts have been made to identify potential catalysts andoxidative processes to convert methane directly to acetic acid at lowtemperatures in an efficient and inexpensive manner. However, mostexisting catalytic systems and oxidative processes to convert methane toacetic acid suffer from high costs and low yields. Furthermore, thesecatalyst systems are homogeneous. For a large scale process like theacetic acid synthesis, a heterogeneous catalyst is preferable. Reportedheterogeneous catalysts like copper-cobalt-based materials, palladium oncarbon or alumina, rhodium on silica and ZrSO₄ show even lower productyield and use higher temperatures (>200° C.) than the homogeneouscatalyst systems. Some progress has been made with homogeneouscatalysts. Recently, Periana et al. demonstrated that Pd^(II) catalyzedthe oxidative carbonylation of methane to acetic acid at 180° C. insulfuric acid, with an approximate yield of 10%. Also, vanadiumcomplexes (e.g, Amavandin complexes or V(O)(acac)₂) have been reportedto be catalytically active in the conversion of methane to acetic acidat 80° C. in trifluoroacetic acid (TFA) as the solvent and potassiumperoxydisulfate (KPS) as the oxidant. These are homogeneous catalyststhat generate low absolute yields corresponding with high TON or viceversa, and lack selectivity. However, no effective heterogeneouscatalyst providing high yields, low TON, and selectivity has yet beendiscovered.

The disclosure provides for a method to replace at least one atom of anorganic molecule with another atom or group of atoms by contacting theorganic molecule with a metal organic framework disclosed herein.Examples of organic molecules that can be modified or acted on, include,but are not limited to, hydrocarbons, hetero-alkanes, hetero-alkenes,hetero-alkynes, heterocycles, alkyl halides, alcohols, carbonyls,amines, aldehydes, ketones, esters, ethers, carboxylic acids, amides,thiols, heterocycles, peroxides and the like. In a certain embodiment,the organic molecule is a hydrocarbon. In a further embodiment, theorganic molecule is a hydrocarbon selected from the group comprisinglinear alkanes, branched alkanes and cycloalkanes. In yet anotherembodiment, the organic molecule is a linear (C₁-C₁₂) alkane.

In another embodiment, the method homolytically cleaves a bond betweenthe atom to be replaced and the organic molecule.

In yet another embodiment, the method heterolytically cleaves a bondbetween the atom to be replaced and the organic molecule.

In a certain embodiment, one or more of the atoms being replaced arehydrogen atoms. In a further embodiment, one or more of the hydrogenatoms being replaced are connected to carbon atoms. In anotherembodiment, one or more of the hydrogen atoms being replaced areconnected to primary carbon atoms. In yet a further embodiment, one ormore of the hydrogen atoms being replaced are connected to a carbon atomof a hydrocarbon molecule. In another embodiment, one or more of thehydrogen atoms being replaced are connected to a carbon atom of analkane. In a certain embodiment, one or more of the hydrogen atoms beingreplaced are connected to a carbon atom of an n-alkane. In yet anotherembodiment, one or more of the hydrogen atoms being replaced areconnected to a carbon atom of a (C₁-C₁₂)alkane. In a further embodiment,one or more of the hydrogen atoms being replaced are connected to acarbon atom of a linear (C₁-C₁₂)-alkane. In another embodiment, one ormore of the hydrogen atoms being replaced are from a methane molecule.In yet another embodiment, one or more of the hydrogen atoms beingreplaced are from an ethane molecule.

In a certain embodiment, one or more of the organic molecule's atoms arebeing replaced with hydrogen, a deuterium, a nonmetal atom or ametalloid atom. In a further embodiment, one or more of the organicmolecule's atoms are replaced with a nonmetal atom. In a yet furtherembodiment, one or more of the organic molecule's atoms are replacedwith a nonmetal atom selected from the following: N, O, F, S, Cl, Se,Br, and I. In another embodiment, one or more of the organic molecule'satoms are replaced with a O, F, Cl, Br or I. In a further embodiment, ahydrogen atom of an alkane is replaced with an O.

In another embodiment, one or more of the organic molecule's atoms arereplaced with a group of atoms containing one or more hydrogens,deuteriums, nonmetal atoms, metalloid atoms, or metals. In a furtherembodiment, one or more of the organic molecule's atoms are replacedwith a functional group which contains more than one atom. In yet afurther embodiment, one or more of the organic molecule's atoms arereplaced with an oxygen containing functional group. In anotherembodiment, one or more of the organic molecule's atoms are replacedwith a hydroxyl, aldehyde, ketone, carboxylic acid, ether, ester, oranhydride. In yet another embodiment, one or more of the organicmolecule's atoms are replaced with a carboxylic acid group. In a furtherembodiment, one or more of the organic molecule's atoms being replacedare replaced with a hydroxyl group.

The disclosure further provides for a method to replace at least oneatom of an organic molecule with another atom or group of atoms in thepresence of carbon monoxide by contacting the organic molecule with ametal organic framework disclosed herein. In a certain embodiment, whenthe method is performed in the presence of carbon monoxide, one or moreof the organic molecule's atoms are replaced with carbon monoxide or alarger functional group resulting from incorporating a carbon monoxidemolecule.

The disclosure further provides for a method to replace at least oneatom of an organic molecule with another atom or group of atoms in thepresence of oxidant by contacting the organic molecule with a metalorganic framework disclosed herein. In a certain embodiment, when themethod is performed in the presence of an oxidant, one or more thehydrogen atoms are replaced with an oxygen and/or an oxygen containingfunctional group. Examples of oxidants, include, but are not limited tohydrogen peroxide and K₂S₂O₈.

The disclosure further provides for a method to replace at least oneatom of an organic molecule with another atom or group of atoms in thepresence of oxidant and in the presence of carbon monoxide by contactingthe organic molecule with a metal organic framework disclosed herein. Ina certain embodiment, when the method is performed in the presence of anoxidant and in the presence of carbon monoxide, one or more of thehydrogen atoms will be replaced with carbon monoxide and/or an oxygencontaining functional group which has incorporated a carbon monoxidemolecule.

In a certain embodiment, the method disclosed herein results inoxidizing an organic molecule. In a further embodiment, the methoddisclosed herein results in converting an alkane to a carboxylic acid.In a certain embodiment, the method disclosed herein converts methaneinto acetic acid. In another embodiment, the method disclosed hereinconverts ethane into propanoic acid or acetic acid. In yet a furtherembodiment, the method disclosed herein converts ethane into propanoicacid.

In a further embodiment, the metal organic framework used in any of themethods above is comprised of a single type of metal or metal ion, and asingle type of linking moiety.

In another embodiment, the metal organic framework is comprised of twoor more different metal and/or metal ions, and a single type of linkingmoiety.

In another embodiment, the metal organic framework is comprised of asingle type of metal or metal ion, and two or more different types oflinking moieties.

In a certain embodiment, a composition comprising a metal organicframework for carrying out the methods disclosed herein. In anotherembodiment, a composition comprising a Formula I containing metalorganic framework for carrying out the methods disclosed herein. In yetanother embodiment, a composition comprising a Formula II containingmetal organic framework for carrying out the methods disclosed herein.In a further embodiment, a composition comprising a vanadium containingmetal organic framework for carrying out the methods disclosed herein.In a further embodiment, a composition comprising a vanadium and FormulaI containing metal organic framework for carrying out the methodsdisclosed herein. In another embodiment, a composition comprising avanadium and Formula II containing metal organic framework for carryingout the methods disclosed herein.

Metals and their associated ions that can be used in the synthesis ofthe metal organic frameworks disclosed herein are selected from thegroup comprising alkali metals, alkaline earth metals, transitionmetals, lanthanoids, actinoids, metalloids, and post transition metals.Metal and/or metal ions can be introduced into open frameworks, MOFs,ZIFs, and COFs, via forming complexes with one or more ligands in aframework or by simple ion exchange. Therefore, it is reasonable toassume that any metal and/or metal ion disclosed herein can beintroduced. Moreover, post synthesis of the framework, metal and/ormetal ions may be exchanged by commonly known techniques, and/oradditional metal ions can be added to the framework by formingcoordination complexes with functional groups arising from postframework reactants.

In an embodiment, one or more metals and/or metal ions that can be usedin the (1) synthesis of frameworks, (2) exchanged post synthesis of theframeworks, and/or (3) added to framework by forming coordinationcomplexes with post framework reactant functional group(s), include, butare not limited to, alkali metals, alkaline earth metals, transitionmetals, lanthanoids, actinoids, metalloids, and post transition metals.

In a certain embodiment, one or more metals and/or metal ions that canbe used in the (1) synthesis of frameworks, (2) exchanged post synthesisof the frameworks, and/or (3) added to framework by forming coordinationcomplexes with post framework reactant functional group(s), include, butare not limited to Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁻,Sc³⁺, Sc²⁺, Sc⁺, Y³⁺, Y²⁺, Y⁺, Ti⁴⁺, Ti³⁺, Ti²⁺, Zr⁴⁺, Zr³⁺, Zr²⁺, Hf⁴⁺,Hf³⁺, V⁵⁻, V⁴⁺, V³⁺, V²⁺, Nb⁵⁺, Nb⁴⁺, Nb³⁺, Nb²⁺, Ta⁵⁺, Ta⁴⁺, Ta³⁺, Ta²,Cr⁶⁺, Cr⁵⁺, Cr⁴⁺, Cr³⁺, Cr²⁺, Cr⁺, Cr, Mo⁶⁺, Mo⁵⁺, Mo⁴⁺, Mo³⁻, Mo²⁺,Mo⁺, Mo, W⁶⁺, W⁵⁺, W⁴⁺, W³⁺, W²⁺, W⁺, W, Mn⁷⁺, Mn⁶⁻, Mn⁵⁺, Mn⁴⁺, Mn³⁺,Mn²⁺, Mn⁺, Re⁷⁺, Re⁶⁺, Re⁵⁺, Re⁴⁺, Re³⁺, Re²⁺, Re⁺, Re, Fe⁶⁺, Fe⁴⁻,Fe³⁺, Fe²⁻, Fe⁺, Fe, Ru⁸⁻, Ru⁷⁺, Ru⁶⁺, Ru⁴⁺, Ru³⁺, Ru²⁺, Os⁸⁺, Os⁷⁺,Os⁶⁺, Os⁵⁺, Os⁴⁺, Os³⁺, Os²⁺, Os⁺, Os, Co⁵⁺, Co⁴⁺, Co³⁻, Co²⁺, Co⁺,Rh⁶⁺, Rh⁵⁺, Rh⁴⁻, Rh³⁺, Rh²⁺, Rh⁺, Ir⁶⁺, Ir⁵⁺, Ir⁴⁺, Ir³⁻, Ir²⁺, Ir⁺,Ir, Ni³⁺, Ni²⁺, Ni⁺, Ni, Pd⁶⁺, Pd⁴⁺, Pd²⁺, Pd⁺, Pd, Pt⁶⁺, Pt⁵⁺, Pt⁴⁺,Pt³⁺, Pt²⁺, Pt⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Ag³⁺, Ag²⁺, Ag⁺, Au⁵⁺, Au⁴⁺,Au³⁺, Au²⁺, Au⁺, Zn²⁺, Zn⁺, Zn, Cd²⁺, Cd⁺, Hg⁴⁺, Hg²⁺, Hg⁺, B³⁺, B²⁺,B⁺, Al³⁺, Al²⁺, Al⁺, Ga³⁺, Ga²⁺, Ga⁺, In³⁺, In²⁺, In¹⁺, Tl³⁺, Tl⁺, Si⁴⁺,Si³⁺, Si²⁺, Si⁺, Ge⁴⁺, Ge³⁺, Ge²⁺, Ge⁺, Ge, Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺,As⁵⁺, As³⁺, As²⁺, As⁺, Sb⁵⁺, Sb³⁺, Bi⁵⁺, Bi³⁺, Te⁶⁺, Te⁵⁺, Te⁴⁺, Te²⁺,La³⁺, La²⁺, Ce⁴⁺, Ce³⁺, Ce²⁺, Pr⁴⁺, Pr³⁺, Pr²⁺, Nd³⁺, Nd²⁺, Sm³⁺, Sm²⁺,Eu³⁺, Eu²⁺, Gd³⁺, Gd²⁺, Gd⁺, Tb⁴⁺, Tb³⁺, Tb²⁺, Tb⁺, Db³⁻, Db²⁺, Ho³⁺,Er³⁺, Tm⁴⁺, Tm³⁺, Tm²⁺, Yb³⁺, Lu³⁺, and any combination thereof, alongwith corresponding metal salt counter-anions.

In a further embodiment, one or more metal ions that can be used in the(1) synthesis of frameworks, (2) exchanged post synthesis of theframeworks, and/or (3) added to framework by forming coordinationcomplexes with post framework reactant functional group(s), include, butare not limited to, Li⁺, Na⁺, Rb⁻, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁻, Ti⁴⁺,Zr⁴⁺, Hf⁴⁻, V⁵⁺, V⁴⁺, V³⁺, V²⁺, Nb³⁺, Ta³⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁻, Mn²⁺,Re³⁺, Re²⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺, Co³⁺, Co²⁺, Rh²⁺, Rh⁺,Ir²⁺, Ir⁺, Ni²⁻, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁻, Ag⁺, Au⁺, Zn²⁺, Cd²⁺,Hg²⁺, Al³⁺, Ga³⁺, In³⁺, Ti³⁺, Si⁴⁺, Si²⁻, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Pb²⁺,Pb⁴⁺, As⁵⁺, As³⁺, As⁻, Sb⁵⁺, Sb³⁺, Sb⁺, Bi⁵⁺, Bi³⁺, and combinationsthereof, along with corresponding metal salt counter-anions.

In yet a further embodiment, one or more metal ions that can be used inthe (1) synthesis of frameworks, (2) exchanged post synthesis of theframeworks, and/or (3) added to framework by forming coordinationcomplexes with post framework reactant functional group(s), include, butare not limited to, Li⁺, Na⁺, Rb⁻, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁻, Ti⁴⁺,Zr⁴⁺, Ta³⁻, V⁵⁺, V⁴⁺, V³⁺, V²⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁻, Fe³⁺, Fe²⁺, Ru³⁺,Ru²⁺, Os³⁺, Os²⁺, Co³⁺, Co²⁺, Ni²⁺, Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺,Cu⁺, Au⁺, Zn²⁺, Al³⁻, Ga³⁺, In³⁺, Si⁴⁺, Si²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺,Bi⁵⁺, Bi³⁺, and any combination thereof, along with corresponding metalsalt counter-anions.

In a certain embodiment, one or more metal ions used in the (1)synthesis of frameworks, (2) exchanged post synthesis of the frameworks,and/or (3) added to framework by forming coordination complexes withpost framework reactant functional group(s), include, but are notlimited to, Sc³⁺, Sc²⁺, Sc⁺, Ti⁴⁺, Ti³⁺, Ti²⁺, Pd⁶, Pd⁴⁺, Pd²⁺, Pd⁺, Pd,Pt⁶⁺, Pt⁵⁺, Pt⁴⁺, Pt³⁺, Pt²⁺, Pt⁺, Fc⁶⁺, Fc⁴⁺, Fc³⁺, Fc²⁺, Fc⁺, Fc,Hg⁴⁺, Hg²⁺, Hg⁺, Cu⁴⁺, Cu³⁺, Cu²⁺, Cu⁺, Al³⁺, Al²⁺, Al⁺, Co⁵⁺, Co⁴⁺,Co³⁺, Co²⁺, Co⁺, Rh⁶⁺, Rh⁵⁺, Rh⁴⁺, Rh³⁺, Rh²⁺, Rh⁺, Ir⁶⁺, Ir⁵⁺, Ir⁴⁺,Ir³⁺, Ir²⁺, Ir⁺, Ir, V⁵⁺, V⁴⁺, V³⁻, and V²⁺.

In another embodiment, one or more metal ions in the (1) synthesis offrameworks, (2) exchanged post synthesis of the frameworks, and/or (3)added to framework by forming coordination complexes with post frameworkreactant functional group(s), is a vanadium ion selected from the groupcomprising V⁵⁺, V⁴⁺, V³⁺, and V²⁺.

In a certain embodiment, the metal ion used in the synthesis of themetal organic framework is a vanadium ion selected from the groupcomprising V⁵⁺, V⁴⁺, V³⁺, and V²⁺.

Linking moiety ligands and/or post frameworks reactants ligands can beselected based on Hard Soft Acid Base theory (HSAB) to optimize theinteraction between the ligands and a metal or metal ion disclosedherein. In certain cases the metal and ligands are selected to be a hardacid and hard base, wherein the ligands and the metals will have thefollowing characteristics: small atomic/ionic radius, high oxidationstate, low polarizability, hard electronegativity (bases),highest-occupied molecular orbitals (HOMO) of the hard base is low inenergy, and lowest unoccupied molecular orbitals (LUMO) of the hard acidare of high energy. Generally hard base ligands contain oxygen. Typicalhard metal and metal ions include alkali metals, and transition metalssuch as Fe, Cr, and V in higher oxidation states. In other cases themetal and ligands are selected to be a soft acid and a soft base,wherein the ligands and the metal or metal ions will have the followingcharacteristics: large atomic/ionic radius, low or zero oxidation state,high polarizability, low electronegativity, soft bases have HOMO ofhigher energy than hard bases, and soft acids have LUMO of lower energythan hard acids. Generally soft base ligands contain sulfur,phosphorous, and larger halides. In other cases the metal and ligandsare selected to be a borderline acid and a borderline base. In certaincases, the metal and ligands are selected so that they are hard andsoft, hard and borderline, or borderline and soft.

In an embodiment, the metal and/or metal ion that can be used in the (1)synthesis of the metal organic frameworks, (2) exchanged post synthesisof the metal organic frameworks, and/or (3) added to the metal organicframework by forming coordination complexes with post framework reactantfunctional group(s) is a HSAB hard metal and/or metal ion. In yetfurther embodiments, the metal and/or metal ion that can be used in the(1) synthesis of frameworks, (2) exchanged post synthesis of theframeworks, and/or (3) added to framework by forming coordinationcomplexes with post framework reactant functional group(s) is a HSABsoft metal and/or metal ion. In even further embodiments, the metaland/or metal ion that can be used in the (1) synthesis of the metalorganic frameworks, (2) exchanged post synthesis of the metal organicframeworks, and/or (3) added to the metal organic framework by formingcoordination complexes with post framework reactant functional group(s)is a HSAB borderline metal and/or metal ion. In the case that there is aplurality of metal and/or metal ions used in the (1) synthesis of themetal organic frameworks, (2) exchanged post synthesis of the metalorganic frameworks, and/or (3) added to the metal organic framework byforming coordination complexes with post framework reactant functionalgroup(s) then there can be any combination of hard, soft and borderlinemetals and/or metal ions that can be used in or attached to the metalorganic framework.

In a further embodiment, one or more metals and/or metal ions that canbe used in the (1) synthesis of the frameworks, (2) exchanged postsynthesis of the frameworks, and/or (3) added to the frameworks byforming coordination complexes with post framework reactant functionalgroup(s) has a coordination number selected from the following: 2, 4, 6,and 8. In another embodiment, one or more metals and/or metal ions has acoordination number of 4 and 6. In yet another embodiment, the metaland/or metal ions has a coordination number of 6.

In a further embodiment, the metal and/or metal ion used in thesynthesis of the the metal organic frameworks can be coordinated withatoms, groups of atoms, or ligands so that the coordination complex orcluster has a molecular geometry including, but not limited to, trigonalplanar, tetrahedral, square planar, trigonal bipyramidal, squarepyramidal, octahedral, trigonal prismatic, pentagonal bipyramidal,paddle-wheel and square antiprismatic. In a further embodiment, themetal ion used in the synthesis of the metal organic frameworks can forma coordination complex or cluster that has a molecular geometryincluding, but not limited to, tetrahedral, paddle-wheel and octahedralmolecular geometry. In a further embodiment, the metal and/or metal ionused in the synthesis of the metal organic framework can form acoordination complex or cluster that has octahedral molecular geometry.In another embodiment, the coordination complex with octahedral geometrycan exist as various isomers depending on whether two or more types ofligands are coordinated to a metal ion. Examples of such isomers thatcan result, include, but are not limited to, cis, trans, fac, mer, andany combination thereof for coordination complexes that have three ormore different ligands. In a yet further embodiment, the coordinationcomplex or cluster disclosed herein may have chirality. In anotherembodiment, the coordination complex or cluster disclosed herein may nothave chirality.

In one embodiment, the linking moiety comprises an organic-based parentchain comprising alkyl, hetero-alkyl, alkenyl, hetero-alkenyl, alkynyl,hetero-alkynyl, one or more cycloalkyl rings, one or more cycloalkenylrings, one or more cycloalkynyl rings, one of more aryl rings, one ormore heterocycle rings, or any combination of the preceding groups,including larger ring structures composed of linked and/or fused ringsystems of different types of rings; wherein this organic-based parentchain may be further substituted with one or more functional groups,including additional substituted or unsubstituted hydrocarbons andheterocycle groups, or a combination thereof; and wherein the linkingmoiety contains at least one (e.g., 1, 2, 3, 4, 5, 6, . . . ) linkingcluster.

In a yet further embodiment, the linking moiety of the metal organicframework has an organic-based parent chain that is comprised of one ormore substituted or unsubstituted rings; wherein one or more of theserings is further substituted with one or more functional groups,including additional substituted or unsubstituted hydrocarbons andheterocycle groups, or a combination thereof; and wherein the linkingmoiety contains at least one (e.g. 1, 2, 3, 4, 5, 6, . . . ) linkingcluster.

In a yet further embodiment, the linking moiety of the metal organicframework has an organic-based parent chain that is comprised of one ormore substituted or unsubstituted rings; wherein one or more of theserings are further substituted with one or more functional groups,including additional substituted or unsubstituted hydrocarbons andheterocycle groups, or a combination thereof; and wherein the linkingmoiety contains at least one (e.g. 1, 2, 3, 4, 5, 6, . . . ) linkingcluster that is either a carboxylic acid, amine, thiol, cyano, nitro,hydroxyl, or heterocycle ring heteroatom, such as the N in pyridine.

In another embodiment, the linking moiety of the metal organic frameworkhas an organic-based parent chain that is comprised of one or moresubstituted or unsubstituted rings; wherein one or more of these ringsare further substituted with one or more functional groups, includingadditional substituted or unsubstituted hydrocarbons and heterocyclegroups, or a combination thereof; and wherein the linking moietycontains at least one (e.g. 1, 2, 3, 4, 5, 6, . . . ) linking clusterthat is either a carboxylic acid, amine, hydroxyl, or heterocycle ringheteroatom, such as the N in pyridine.

In another embodiment, the linking moiety of the metal organic frameworkhas an organic-based parent chain that is comprised of one or moresubstituted or unsubstituted rings; wherein one or more of these ringsare further substituted with one or more functional groups, includingadditional substituted or unsubstituted hydrocarbons and heterocyclegroups, or a combination thereof; and wherein the linking moietycontains at least one (e.g. 1, 2, 3, 4, 5, 6, . . . ) carboxylic acidlinking cluster.

In another embodiment, the linking moiety of the metal organic frameworkhas an organic-based parent chain that is comprised of one or moresubstituted or unsubstituted rings; wherein one or more of these ringsare further substituted with two or more functional groups, includingadditional substituted or unsubstituted hydrocarbon and heterocyclegroups, or a combination thereof; and wherein the linking moietycontains at least two (e.g. 2, 3, 4, 5, 6, . . . ) carboxylic acidlinking clusters.

In certain embodiments, the metal organic framework is generated fromone or more linking moieties that have a structure of Formula I, II,III, IV, V, VI, VII, VIII, IX, and X:

wherein:

R¹-R⁴, R¹⁵-R²⁰, R²³-R³⁰, R³⁸-R⁹⁶ are independently selected from thegroup comprising H, FG, (C₁-C₂₀)alkyl, substituted (C₁-C₂₀)alkyl,(C₁-C₂₀)alkenyl, substituted (C₁-C₂₀)alkenyl, (C₁-C₂₀)alkynyl,substituted (C₁-C₂₀)alkynyl, hetero-(C₁-C₂₀)alkyl, substitutedhetero-(C₁-C₂₀)alkyl, hetero-(C₁-C₂₀)alkenyl, substitutedhetero-(C₁-C₂₀)alkenyl, hetero-(C₁-C₂₀)alkynyl, substitutedhetero-(C₁-C₂₀)alkynyl, (C₁-C₂₀)cycloalkyl, substituted(C₁-C₂₀)cycloalkyl, aryl, substituted aryl, heterocycle, substitutedheterocycle, —C(R⁵)₃, —CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶,—OC(R⁵)₃, —OCH(R⁵)₂, —OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

wherein R¹ and R³ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle, wherein R² and R⁴ are linked together to form asubstituted or unsubstituted ring selected from the group comprisingcycloalkyl, aryl and heterocycle, wherein R¹⁸ and R¹⁹ are linkedtogether to form a substituted or unsubstituted ring selected from thegroup comprising cycloalkyl, aryl and heterocycle, wherein R²⁴ and R²⁵are linked together to form a substituted or unsubstituted ring selectedfrom the group comprising cycloalkyl, aryl and heterocycle, and whereinR²⁸ and R²⁹ are linked together to form a substituted or unsubstitutedring selected from the group comprising cycloalkyl, aryl andheterocycle;

R⁵ is selected from the group comprising FG, (C₁-C₂₀)alkyl,(C₁-C₂₀)substituted alkyl, ((C₁-C₂₀)alkenyl, substituted(C₁-C₂₀)alkenyl, (C₁-C₂₀)alkynyl, substituted (C₁-C₂₀)alkynyl,hetero-(C₁-C₂₀)alkyl, substituted hetero-(C₁-C₂₀)alkyl,hetero-(C₁-C₂₀)alkenyl, substituted hetero-(C₁-C₂₀)alkenyl,hetero-(C₁-C₂₀)alkynyl, substituted hetero-(C₁-C₂₀)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is one or more substituted or unsubstituted rings selected from thegroup comprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 10.

In another embodiment, the metal organic framework is generated fromlinking moieties that have at least two structures selected from FormulaI, II, III, IV, V, VI, VII, VIII, IX, and X.

In a further embodiment, the metal organic framework is generated from alinking moiety that has the structure of Formula I, II, III, IV, V, VI,VII, and VIII. In yet a further embodiment, the metal organic frameworkis generated from linking moieties that have at least two structuresselected from Formula I, II, III, IV, V, VI, VII, and VIII.

In another embodiment, the metal organic framework is generated from alinking moiety that has a structure of Formula IX or X. In anotherembodiment, the metal organic framework is generated from linkingmoieties that have structures of Formula IX and X.

In a further embodiment, the metal organic framework is generated from alinking moiety comprising Formula I, II, III, IV, V, VI, VII, VIII, IX,and X:

wherein:

R¹-R⁴, R¹⁵-R²⁰, R²³-R³⁰, R³⁸-R⁹⁶ are independently selected from thegroup comprising H, FG, (C₁-C₆)alkyl, substituted (C₁-C₆)alkyl,(C₁-C₆)alkenyl, substituted (C₁-C₆)alkenyl, (C₁-C₆)alkynyl, substituted(C₁-C₆)alkynyl, hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₁-C₆)alkenyl,hetero-(C₁-C₆)alkynyl, substituted hetero-(C₁-C₆)alkynyl,(C₁-C₆)cycloalkyl, substituted (C₁-C₆)cycloalkyl, aryl, substitutedaryl, heterocycle, substituted heterocycle, —C(R⁵)₃, —CH(R⁵)₂, —CH₂R⁵,—C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂, —OCH₂R⁵, —OC(R⁶)₃,—OCH(R⁶)₂, —OCH₂R⁶,

wherein R¹ and R³ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle, wherein R² and R⁴ are linked together to form asubstituted or unsubstituted ring selected from the group comprisingcycloalkyl, aryl and heterocycle, wherein R¹⁸ and R¹⁹ are linkedtogether to form a substituted or unsubstituted ring selected from thegroup comprising cycloalkyl, aryl and heterocycle, wherein R²⁴ and R²⁵are linked together to form a substituted or unsubstituted ring selectedfrom the group comprising cycloalkyl, aryl and heterocycle, and whereinR²⁸ and R²⁹ are linked together to form a substituted or unsubstitutedring selected from the group comprising cycloalkyl, aryl andheterocycle;

R⁵ is selected from the group comprising FG, (C₁-C₆)alkyl,(C₁-C₆)substituted alkyl, ((C₁-C₆)alkenyl, substituted (C₁-C₆)alkenyl,(C₁-C₆)alkynyl, substituted (C₁-C₆)alkynyl, hetero-(C₁-C₆)alkyl,substituted hetero-(C₁-C₆)alkyl, hetero-(C₁-C₆)alkenyl, substitutedhetero-(C₁-C₆)alkenyl, hetero-(C₁-C₆)alkynyl, substitutedhetero-(C₁-C₆)alkynyl, hemiacetal, hemiketal, acetal, ketal, andorthoester;

R₆ is one or more substituted or unsubstituted rings selected from thegroup comprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In a certain embodiment, the metal organic framework is generated from alinking moiety comprising structural Formula I:

wherein:

R¹-R⁴ are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶

wherein R¹ and R³ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle, and wherein R² and R⁴ are linked together to form asubstituted or unsubstituted ring selected from the group comprisingcycloalkyl, aryl and heterocycle;

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is one or more substituted or unsubstituted rings selected from thegroup comprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In another embodiment, the metal organic framework is generated from alinking moiety selected from the group comprising:

In yet another embodiment, the metal organic framework is generated froma linking moiety selected from the group comprising:

In yet another embodiment, the metal organic framework is generated froma linking moiety of:

In yet another embodiment, the metal organic framework is generated froma linking moiety of:

In a further embodiment, the linking moiety of structural Formula Iwherein R² and R⁴ are linked together to form a unsubstituted orsubstituted aryl comprising structural Formula I(a):

wherein:

R¹, R³, R⁷-R¹⁰ are independently selected from the group comprising H,halo, amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H,AsO₄H, P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃,Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶.

and wherein R¹ and R³ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle;

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is one or more substituted or unsubstituted rings selected from thegroup comprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In a yet further embodiment, the linking moiety of structural Formula Iwherein R² and R⁴ are linked together to form a unsubstituted orsubstituted aryl and wherein R¹ and R³ are linked together to form aunsubstituted or substituted aryl, comprising structural Formula I(b):

wherein:

R⁷-R¹⁴ are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is one or more substituted or unsubstituted rings selected from thegroup comprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In one embodiment, the metal organic framework is generated from alinking moiety of Formula II:

wherein:

R¹⁵-R²⁰ are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

and wherein R¹⁸ and R¹⁹ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle;

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is a substituted or unsubstituted ring selected from the groupcomprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In an another embodiment, the linking moiety of structural Formula IIwherein R¹⁸ and R¹⁹ are linked together to form a unsubstituted orsubstituted aryl comprising structural Formula II(a):

wherein:

R¹⁵-R¹⁷, R²⁰-R²² are independently selected from the group H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃. —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is one or more substituted or unsubstituted rings selected from thegroup comprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In an another embodiment, the metal organic framework is generated froma linking moiety of Formula III:

wherein:

R²³-R³⁰ are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

wherein R²⁴ and R²⁵ are linked together to form a substituted orunsubstituted ring selected from the group comprising cycloalkyl, aryland heterocycle, and wherein R²⁸ and R²⁹ are linked together to form asubstituted or unsubstituted ring selected from the group comprisingcycloalkyl, aryl and heterocycle;

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is a substituted or unsubstituted ring selected from the groupcomprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In a further embodiment, the linking moiety of structural Formula IIIwherein R²⁴ and R²⁵ are linked together to form a unsubstituted orsubstituted aryl, and wherein R²⁸ and R²⁹ are linked together to form aunsubstituted or substituted aryl to comprise structural Formula III(a):

wherein:

R²⁶, R²⁹, R³⁰, R³³, R³⁴-R³⁷ are independently selected from the groupcomprising H, halo, amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄,Ge(SH)₄, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃,Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃,As(SH)₃, (C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is a substituted or unsubstituted ring selected from the groupcomprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In a yet further embodiment, the metal organic framework is generatedfrom a linking moiety of Formula IV:

wherein:

R³⁸-R⁴⁰ are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is a substituted or unsubstituted ring selected from the groupcomprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In a certain embodiment, the metal organic framework is generated from alinking moiety of Formula V:

wherein:

R⁴¹-R⁵² are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is a substituted or unsubstituted ring selected from the groupcomprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In an another embodiment, the metal organic framework is generated froma linking moiety of Formula VI:

wherein:

R⁵³-R⁶⁷ are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is a substituted or unsubstituted ring selected from the groupcomprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In an another embodiment, the metal organic framework is generated froma linking moiety of Formula VII:

wherein:

R⁶⁸-R⁸² are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is a substituted or unsubstituted ring selected from the groupcomprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In an another embodiment, the metal organic framework is generated froma linking moiety of Formula III:

wherein:

R⁸³-R⁸⁸ are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

R⁵ is selected from the group comprising hydroxyl, amine, thiol, cyano,carboxyl, (C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl,substituted (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester;

R₆ is a substituted or unsubstituted ring selected from the groupcomprising cycloalkyl, aryl, and heterocycle; and

X is a number from 0 to 3.

In another embodiment, the metal organic framework is generated from alinking moiety of Formula IX:

wherein:

Z is either a C or N;

R⁸⁹-R⁹¹ are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₁-C₆)alkenyl, (C₁-C₆)alkynyl, substituted (C₁-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl, hetero-(C₁-C₆)alkenyl, substituted hetero-(C₁-C₆)alkenyl, hetero-(C₁-C₆)alkynyl,substituted hetero-(C₁-C₆)alkynyl, aryl, substituted aryl, heterocycle,substituted heterocycle, and are absent when Z is an N.

In yet another embodiment, the linking moiety of Formula IX is selectedfrom the group comprising:

In another embodiment, the metal organic framework is generated from alinking moiety of Formula X:

wherein:

Z is either a C or N;

R⁹²-R⁹⁶ are independently selected from the group comprising H, halo,amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, AsO₃H, AsO₄H,P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃,Si(SH)₄, Ge(SH)₄, Sn(SH)₄, PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₁-C₆)alkenyl, (C₁-C₆)alkynyl, substituted (C₁-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl, hetero-(C₁-C₆)alkenyl, substituted hetero-(C₁-C₆)alkenyl, hetero-(C₁-C₆)alkynyl,substituted hetero-(C₁-C₆)alkynyl, aryl, substituted aryl, heterocycle,substituted heterocycle, and are absent when Z is an N.

In yet another embodiment, the linking moiety of Formula X is selectedfrom the group comprising:

The preparation of the frameworks of the disclosure can be carried outin either an aqueous or non-aqueous solvent system. The solvent may bepolar or non-polar, or a combination thereof, as the case may be. Thereaction mixture or suspension comprises a solvent system, linkingmoiety or moieties, and a metal or a metal/salt complex. The reactionsolution, mixture or suspension may further contain a templating agent,catalyst, or combination thereof. The reaction mixture may be heated atan elevated temperature or maintained at ambient temperature, dependingon the reaction components.

Examples of non-aqueous solvents that can be used in the reaction tomake the framework and/or used as non-aqueous solvent for a postsynthesized framework reaction, include, but is not limited to:n-hydrocarbon based solvents, such as pentane, hexane, octadecane, anddodecane; branched and cyclo-hydrocarbon based solvents, such ascycloheptane, cyclohexane, methyl cyclohexane, cyclohexene,cyclopentane; aryl and substituted aryl based solvents, such as benzene,toluene, xylene, chlorobenzene, nitrobenzene, cyanobenzene, naphthalene,and aniline; mixed hydrocarbon and aryl based solvents, such as, mixedhexanes, mixed pentanes, naptha, and petroleum ether; alcohol basedsolvents, such as, methanol, ethanol, n-propanol, isopropanol, propyleneglycol, 1,3-propanediol, n-butanol, isobutanol, 2-methyl-1-butanol,tert-butanol, 1,4-butanediol, 2-methyl-1-petanol, and 2-pentanol; amidebased solvents, such as, dimethylacetamide, dimethylformamide (DMF),formamide, N-methylformamide, N-methylpyrrolidone, and 2-pyrrolidone;amine based solvents, such as, piperidine, pyrrolidine, collidine,pyridine, morpholine, quinoline, ethanolamine, ethylenediamine, anddiethylenetriamine; ester based solvents, such as, butylacetate,sec-butyl acetate, tert-butyl acetate, diethyl carbonate, ethyl acetate,ethyl acetoacetate, ethyl lactate, ethylene carbonate, hexyl acetate,isobutyl acetate, isopropyl acetate, methyl acetate, propyl acetate, andpropylene carbonate; ether based solvents, such as, di-tert-butyl ether,diethyl ether, diglyme, diisopropyl ether, 1,4-dioxane,2-methyltetrahydrofuran, tetrahydrofuran (THF), and tetrahydropyran;glycol ether based solvents, such as, 2-butoxyethanol, dimethoxyethane,2-ethoxyethanol, 2-(2-ethoxyethoxy)ethanol, and 2-methoxyethanol;halogenated based solvents, such as, carbon tetrachloride,cholorbenzene, chloroform, 1,1-dichloroethane, 1,2-dichloroethane,1,2-dichloroethene, dichloromethane (DCM), diiodomethane,epichlorohydrin, hexachlorobutadiene, hexafluoro-2-propanol,perfluorodecalin, perfluorohexane, tetrabromomethane,1,1,2,2-tetrchloroethane, tetrachloroethylene, 1,3,5-trichlorobenzene,1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene,1,2,3-trichloropropane, trifluoroacetic acid, and2,2,2-trifluoroethanol; inorganic based solvents, such as hydrogenchloride, ammonia, carbon disulfide, thionyl chloride, and phophoroustribromide; ketone based solvents, such as, acetone, butanone,ethylisopropyl ketone, isophorone, methyl isobutyl ketone, methylisopropyl ketone, and 3-pentanone; nitro and nitrile based solvents,such as, nitroethane, acetonitrile, and nitromethane; sulfur basedsolvents, dimethyl sulfoxide (DMSO), methylsulfonylmethane, sulfolane,isocyanomethane, thiophene, and thiodiglycol; urea, lactone andcarbonate based solvents, such as1-3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU),1-3-dimethyl-2-imidazolidinone, butyrolactone, cis-2,3-butylenecarbonate, trans-2,3-butylene carbonate, 2,3-butylene carbonate;carboxylic acid based solvents, such as formic acid, acetic acid,chloracetic acid, trichloroacetic acid, trifluoroacetic acid, propanoicacid, butanoic acid, caproic acid, oxalic acid, and benzoic acid; boronand phosphorous based solvents, such as triethyl borate, triethylphosphate, trimethyl borate, and trimethyl phosphate; deuteriumcontaining solvents, such as deuterated acetone, deuterated benzene,deuterated chloroform, deuterated dichloromethane, deuterated DMF,deuterated DMSO, deuterated ethanol, deuterated methanol, and deuteratedTHF; and any appropriate mixtures thereof.

In another embodiment, the nonaqueous solvent used as the solvent systemin synthesizing the framework has a pH less than 7. In a furtherembodiment, the solvent system used to synthesize the framework is anaqueous solution that has a pH less than 7. In yet a further embodiment,the solvent system used to synthesize the frameworks contains water. Inanother embodiment, the solvent system used to synthesize the frameworkscontains water and hydrochloric acid.

Those skilled in the art will be readily able to determine anappropriate solvent or appropriate mixture of solvents based on thestarting reactants and/or where the choice of a particular solvent(s) isnot believed to be crucial in obtaining the materials of the disclosure.

Templating agents can be used in the methods of the disclosure.Templating agents employed in the disclosure are added to the reactionmixture for the purpose of occupying the pores in the resultingcrystalline base frameworks. In some variations of the disclosure,space-filling agents, adsorbed chemical species and guest speciesincrease the surface area of the metal-organic framework. Suitablespace-filling agents include, for example, a component selected from thegroup consisting of: (i) alkyl amines and their corresponding alkylammonium salts, containing linear, branched, or cyclic aliphatic groups,having from 1 to 20 carbon atoms; (ii) aryl amines and theircorresponding aryl ammonium salts having from 1 to 5 phenyl rings; (iii)alkyl phosphonium salts, containing linear, branched, or cyclicaliphatic groups, having from 1 to 20 carbon atoms; (iv) arylphosphonium salts, having from 1 to 5 phenyl rings; (v) alkyl organicacids and their corresponding salts, containing linear, branched, orcyclic aliphatic groups, having from 1 to 20 carbon atoms; (vi) arylorganic acids and their corresponding salts, having from 1 to 5 phenylrings; (vii) aliphatic alcohols, containing linear, branched, or cyclicaliphatic groups, having from 1 to 20 carbon atoms; or (viii) arylalcohols having from 1 to 5 phenyl rings.

In certain embodiments templating agents are used with the methodsdisclosed herein, and in other embodiments templating agents are notused with the methods disclosed herein.

Crystallization of the frameworks can be carried out by maintaining thesolution, mixture, or suspension at ambient temperature or bymaintaining the solution, mixture, or suspension at an elevatedtemperature; adding a diluted base to the solution; diffusing thediluted base throughout the solution; and/or transferring the solutionto a closed vessel and heating to a predetermined temperature.

In a certain embodiment, crystallization of the frameworks can beimproved by adding an additive that promotes nucleation.

In a certain embodiment, the solution, mixture or suspension ismaintained at ambient temperature to allow for crystallization. Inanother embodiment, the solution, mixture, or suspension is heated inisothermal oven for up to 300° C. to allow for crystallization. In yetanother embodiment, activated frameworks can be generated bycalcination. In a further embodiment, calcination of the frameworks canbe achieved by heating the frameworks at 350° C. for at least 1 hour.

It is further contemplated that a framework of the disclosure may begenerated by first utilizing a plurality of linking moieties havingdifferent functional groups, wherein at least one of these functionalgroups may be modified, substituted, or eliminated with a differentfunctional group post-synthesis of the framework. In other words, atleast one linking moiety comprises a functional group that may bepost-synthesized reacted with a post framework reactant to furtherincrease the diversity of the functional groups in the organicframework.

After the frameworks are synthesized, the frameworks may be furthermodified by reacting with one or more post framework reactants that mayor may not have denticity. In a certain embodiment, the frameworksas-synthesized are not reacted with a post framework reactant. Inanother embodiment, the frameworks as-synthesized are reacted with atleast one post framework reactant. In yet another embodiment, theframeworks as-synthesized are reacted with at least two post frameworkreactants. In a further embodiment, the frameworks as-synthesized arereacted with at least one post framework reactant that will result inadding denticity to the framework.

It is contemplated by this disclosure that chemical reactions thatmodify, substitute, or eliminate a functional group post-synthesis ofthe framework with post framework reactant may use one or more similaror divergent chemical reaction mechanisms depending on the type offunctional group and/or post framework reactant used in the reaction.Examples of chemical reaction mechanisms contemplated by this inventioninclude, but is not limited to, radical-based, unimolecular nuclephilicsubstitution (SN1), bimolecular nucleophilic substitution (SN2),unimolecular elimination (E1), bimolecular elimination (E2), E1cBelimination, nucleophilic aromatic substitution (SnAr), nucleophilicinternal substitution (SNi), nucleophilic addition, electrophilicaddition, oxidation, reduction, cycloadition, ring closing metathesis(RCM), pericylic, electrocylic, rearrangement, carbene, carbenoid, crosscoupling, and degradation.

All the aforementioned linking moieties that possess appropriatereactive functionalities can be chemically transformed by a suitablereactant post framework synthesis to add further functionalities to thepores. By modifying the organic links within the frameworkpost-synthetically, access to functional groups that were previouslyinaccessible or accessible only through great difficulty and/or cost ispossible and facile.

It is yet further contemplated by this disclosure that to enhancechemoselectivity it may be desirable to protect one or more functionalgroups that would generate unfavorable products upon a chemical reactiondesired for another functional group, and then deprotect this protectedgroup after the desired reaction is completed. Employing such aprotection/deprotection strategy could be used for one or morefunctional groups.

Other agents can be added to increase the rate of the reactionsdisclosed herein, including adding catalysts, bases, and acids.

In another embodiment, the post framework reactant is selected to have aproperty selected from the group comprising, binds a metal ion,increases the hydrophobicity of the framework, modifies the gas sorptionof the framework, modifies the pore size of the framework, and tethers acatalyst to the framework.

In one embodiment, the post framework reactant can be a saturated orunsaturated heterocycle.

In another embodiment, the post framework reactant has 1-20 carbons withfunctional groups including atoms such as N, S, and O.

In yet another embodiment, the post framework reactant is selected tomodulate the size of the pores in the framework.

In another embodiment, the post framework reactant is selected toincrease the hydrophobicity of the framework.

In yet another embodiment, the post framework reactant is selected tomodulate gas separation of the framework. In a certain embodiment, thepost framework reactant creates an electric dipole moment on the surfaceof the framework when it chelates a metal ion.

In a further embodiment, the post framework reactant is selected tomodulate the gas sorption properties of the framework. In anotherembodiment, the post framework reactant is selected to promote orincrease hydrocarbon gas sorption of the framework.

In yet a further embodiment, the post framework reactant is selected toincrease or add catalytic efficiency to the framework.

In another embodiment, a post framework reactant is selected so thatorganometallic complexes can be tethered to the framework. Such tetheredorganometallic complexes can be used, for example, as heterogeneouscatalysts.

In one embodiment, the disclosure provides highly catalytically activeheterogeneous metal-organic framework (MOF) catalysts [V(O)(C₁₀H₈O₄)]and [V(O)(C₈H₄O₄)] (MOF-V150 and MIL-47, respectively) for the direct,one-step oxidation of methane to acetic acid. These catalysts provide upto 70% yield (490 TON) and are very selective (100%). Both carbon atomsof the acetic acid are directly derived from methane molecules. Thecatalysts are reusable and easy to separate from the products. They arecatalytically active for several recycling steps under mild conditions.

Two vanadium-based MOFs, MOF-V150 and MIL-47, were used as catalysts formethane activation. They were chosen, because their structures aresimilar to vanadium complexes already known to have activity for thisreaction, but as homogeneous catalysts, e.g., Amavandin complexes orV(O)(acac)₂. (FIG. 2). The MOFs are thermally stable up to 400° C. andchemically stable under strong oxidizing conditions, thus making thempromising catalysts for methane activation.

The vanadium MOFs have a secondary building unit (SBU) which iscomprised of an infinite (—O—V—)_(∝) rod (FIG. 2 b) with carboxyl ate Oatoms completing octahedral coordination around V (FIG. 1). Theoctahedra (VO₆) are linked into rods by corner-sharing. The benzenemoieties link these rods into a three-dimensional orthorhombic frameworkcontaining a 1-D pore channel. (FIG. 2 d) MIL-47 includes abenzendicarboxylic (bdc) as a linker, while MOF-V150 is built from the2,5-dimethyl-benzendicarboxylic (mbdc) linker. (FIG. 1 and FIG. 2 d)MOF-V150 was obtained by reacting mbdc and vanadium (IV) oxide (VO₂) inhydrochloric acid and water at 220° C. for 3 days. MIL-47 was obtainedby reacting bdc with vanadium (III) chloride (VCI₃) in water at 200° C.for 3 days. Activated materials resulted from removing guest moleculesin the pores by calcination of the as-synthesized samples at 350° C. inair for 8 hours. Type I nitrogen sorption of the activated MOFs revealstheir microporous characteristics. Six different MOF samples wereprepared: as-synthesized MOF-V150, partially activated MOF-V150 with asurface area of 100 m²/g and 200 m²/g, as-synthesized MIL-47, partiallyactivated MIL-47 with a surface area of 350 m²/g and 500 m²/g. For thedirect conversion of methane to acetic acid, each of these MOF sampleswere used as a catalyst and tested under the same reaction conditions.

It was found, in the absence of CO, that methane was converted to aceticacid in up to 70% yields, corresponding to up to 175 TON, in reactionswhere MOF-V150 and MIL-47 were the heterogeneous catalysts, KPS was theoxidant and TFA was the solvent. In the presence of CO, these MOFs giveup to 49% yield corresponding to up to 490 TON (Reaction 1, 2 and Table1, 2).

TABLE 1 Catalytic activity of heterogeneous MOF catalysts in theconversion of methane to acetic acid in the absence of CO. Surface TMarea AcOH TM Yield (%) select ^([e]) TON ^([g]) Catalyst ^([a]) (m²g⁻¹)(mM) (mM) AcOH ^([b]) TM ^([c]) Total ^([d]) (%) (AcOH) MOF-V150-I —0.36 0.07 36 1.8 38 17 89 MOF-V150-II 100 0.38 0.30 38 6.0 44 29 95MOF-V150-III 200 0.48 0.30 48 7.5 56 38 121 MIL-47-IV — 0.38 0.08 38 2.040 18 94 MIL-47-V 350 0.60 0.08 60 2.0 62 11 150 MIL-47-VI 500 0.70 0.0770 1.8 72 9 175 ^([a]) Reaction conditions: At ambient temperature, 10bars of CH₄ pressure was introduced to a mixture containing, a MOFcatalyst, K₂S₂O₈ (4 mmol), and TFA (7.5 ml). The mixture was then heatedat 80° C. for 20 hrs. ^([b]) AcOH yield was calculated as {(4 ×[CH₃CO₂H])/[K₂S₂O₈]}. ^([c]) TM yield was calculated as([CF₃CO₂CH₃]/[K₂S₂O₈]). ^([d]) Total yield was calculated as {(4 ×[CH₃CO₂H]) + [CF₃CO₂CH₃])/[K₂S₂O₈]} (excluding gaseous products). ^([e])TM selectivity was calculated as the molar ratio of AcOH to the totalmolar yield of products excluding gaseous products. ^([g]) TON wascalculated as the molar ratio of acetic acid to the metal content. Agaseous product is predominately CO₂, as determined by GC. With respectto surface area, a dash (—) indicate an as-synthesized sample.

TABLE 2 Catalytic activity of heterogeneous MOF catalysts in theconversion of methane to acetic acid in the presence of CO (100%selectivity towards acetic acid). Surface area AcOH Total TON^([d])Catalysts^([a]) (m²g⁻¹) (mM) yield(%)^([b]) (AcOH) MOF-V150-I — 1.36 34340 MOF-V150-II 100 1.75 44 440 MOF-V150-III 200 1.95 49 490 MIL-47-IV —0.95 24 240 MIL-47-V 350 1.16 29 290 MIL-47-VI 500 1.32 33 330 VOSO₄ —0.8 21 210 ^([a])Reaction conditions: At ambient temperature, 10 bars ofCH₄ pressure (25° C.) and 10 bars of CO pressure were introduced to amixture containing a MOF catalyst, K₂S₂O₈ (4 mmol), and TFA (7.5 ml).The mixture was then heated at 80° C. for 20 hrs. ^([b])Total yield wascalculated as ([CH₃CO₂H]/[K₂S₂O₈]) (excluding gaseous products).^([c])AcOH selectivity was calculated as the molar ratio of AcOH to thetotal molar yield of products excluding gaseous products. ^([d])TON wascalculated as the molar ratio of AcOH to the metal content. A gaseousproduct is predominately CO₂, as determined by GC. With respect tosurface area, a dash (—) indicate an as-synthesized sample.

In the absence of CO, the major products are acetic acid together withthe methyl ester of TFA (trifluoro methyl acetate, TM). Catalysts MIL-47and MOF-V150 provide 70% and 48% acetic acid yield, respectively. (Table1). When the catalytic reaction is performed using activated materials,the reaction yields more AcOH (72%) in comparison to the as-synthesizedmaterials (40%). (Table 1, lines 6 and 4). The more open pores of theactivated materials lead to a higher product yield, since there are moreactive centers exposed. Unexpectedly, although the coordinationenvironment of vanadium is the same in both catalysts, MOF-V150 giveshigher TM selectivity (38%) than MIL-47 (18%). (Table 1, lines 3 and 4).The presence of two methyl groups in the linker of MOF-V150 creates amore hydrophobic environment within the pores, which might facilitatethe formation of the less polar products such as esters. The hydrophobiceffect of MOF-V150 is more apparent when the frameworks are activated.The activated sample of MOF-V150 gives significantly higher esterselectivity (38%) compared to the as-synthesized sample (17%). (Table 1,lines 3 and 1). This behavior was not observed in MIL-47.

Reducing the amount of oxidant consumed would elevate the economicfeasibility of the finding. Although the MOFs give a high yield of AcOH,the reaction consumes four moles of K₂S₂O₈ for one mole of AcOH.(Reaction 1). It was investigated whether the reaction in the presenceof CO to attempt to reduce the required amount of oxidant. In thepresence of CO the reaction requires only one mole of the oxidant permole of acetic acid. (Reaction 2). Under otherwise unchanged conditions,the amount of acetic acid found in the reaction mixture increasessignificantly from 0.7 mmol to 2.0 mmol and TON increases from 199 to488 at p(CO)=10 bars (table 2), suggesting CO acts as a carbonylationagent as reported. Now, MOF-V150 is more active compared to MIL-47. Areason for the greater activity can only be speculated. Assuming thereaction takes place at the external surface of the MOFs, MOF-V150 wouldhave a larger amount of accessible active sites per weight because ofits smaller particle size compared to MIL-47. This effect mightcontribute to the catalytic activity of MOF-V150. If the reaction takesplace inside the pores, the pore size or the pore environment ofMOF-V150 might happen to be more suitable for this reaction. MOF-V150has a smaller pore size (9 Å) than MIL-47 (11 Å) and the additionalmethyl groups in MOF-V150 may increase the lipophilicity of thematerial. Notably, the reaction gives 100% selectivity toward aceticacid. (Table 2).

To confirm the origins of the carbon atoms, the reaction was run withand without CO using >99% *¹³C isotopically enriched methane. WithoutCO, 90% of the carbon atoms in the acetic acid product were derived frommethane molecules. The ¹³C NMR spectrum of the crude reaction mixturefrom the reaction of ¹³CH₄ with the MOF catalysts in the absence of COis shown in FIG. 3. The NMR shows a doublet at δ=19.5 ppm (13CH₃—),¹J(¹³C, ¹³C)=57.2 Hz and at δ=177.5 ppm (−¹³CO), ¹J (¹³C, ¹³C)=57.2 Hz.(FIG. 3). This confirmed that a large amount of acetic acid carbon atomsis derived exclusively from methane molecules. In addition, the spectrumshows a singlet at δ=19.3 ppm. (FIG. 3). This singlet indicates thepresence of acetic acid product where 1 carbon is derived from methaneand the other originates from TFA. The amount of this acetic acid in thereaction mixture was quantified by ¹H NMR to be about 10%. In contrast,with homogeneous vanadium catalysts in the absence of CO, only themethyl group in the acetic acid is derived from methane while the CO isreported to be from TFA. When conducting the reaction in the presence ofCO the majority of the acetic acid has the methyl carbon derived frommethane and the carbonyl carbon is derived from CO. The ¹³C NMR spectrumof the crude reaction mixture from this reaction is shown in FIG. 4. Itshows a singlet at δ=20.0 ppm (¹³CH₃—) and a doublet at δ=181 ppm (FIG.4). The methyl group was found to have near quantitative amounts of ¹³Cenrichment, while the coupling with the carbonyl group, having natural¹³C abundance (ca. 1%), was not resolved in the spectrum. Vice versa,the ¹³C carbons in the carbonyl group always demonstrated coupling with¹³C carbon from the methyl group. Therefore, this group is exclusivelyobserved as a doublet corroborating that the acetic acid predominatelyformed in the reaction mixture has one carbon from methane and anotherfrom CO.

The catalytic activities of the MOFs remain almost the same during therecycling experiments. There was no reactivation between the steps. Theyield and TONs remain nearly constant during the last three recyclingsteps (FIG. 5). After an aliquot was taken out for ¹H NMR analysis,recycling experiments were performed by adding more methane, K₂S₂O₈ andTFA to a previous reaction mixture. In addition, it was unexpectedlyfound that acetic acid was not further oxidized during each additionalreaction step. The partial oxidation products from methane are easilyover-oxidized to CO₂. Therefore, stopping the oxidation at acetic acidrequires a highly selective catalyst. (ref) Consequently, the MOFcatalysts of the disclosure are highly selective catalysts. In addition,the MOFs maintain unexpectedly high structural integrity during therecycling, as evidenced by comparing the pxrd patterns between the freshcatalyst and the recycled catalyst (FIG. 6).

Filtration experiments confirmed the true heterogeneous nature of thecatalytic reaction. After the initial experiment, the MOF catalyst wasremoved by filtration. Then, fresh K₂S₂O₈ and TFA were added to thefiltrate. The reaction was then performed with the filtrate under thesame reaction conditions as the initial experiment. No catalyticconversion was observed. This indicates that if there is any leaching ofvanadium ions from the catalysts, the vanadium species resulting therefrom are not catalytically active.

When the experiments are run without a MOF-catalyst or without oxidantsno acetic acid results, indicating that both the oxidant and theMOF-catalyst are required for a productive reaction. A controlexperiment has been carried out with the homogeneous catalyst VOSO₄,which gives 13% and 21% acetic acid yield in the absence and presence ofCO, respectively. Therefore, the MOF catalysts of the disclosure areunexpectedly far more efficient at catalyzing alkane oxidations thansimilar catalysts known in the art (see Table 2).

Although the mechanism is still unknown, it is proposed that theoxidative activation of methane, with K₂S₂O₈ as the oxidizing agent, TFAas the solvent, and in the presence of vanadium catalysts, results fromthe formation of methyl radicals. These methyl radicals would in turnreact with CO to form CH₃CO. radicals. K₂S₂O₈ in the acidic TFA solventcan exist in the protonated form HS₂O₈ ⁻ or the un-protonated form S₂O₈²⁻. Upon thermal decomposition, hydrosulfate or sulfate radicals (HSO₄⁻., SO₄ ⁻.) are formed. (Reaction 3). The formation of TM ester wasreported to be the product of a CH₃. or HSO₄. radical reacting withCF₃COOH to form a CF₃COO. radical. This CF₃COO. radical then reacts withCH₃. to form the TM ester.

The disclosure provides highly active heterogeneous MOF catalysts thatcan directly and selectively activate methane to yield acetic acid in aone-step reaction under mild conditions. The catalysts are stable underthe applied catalytic conditions and are reusable for at least fourrecycling steps. Oxidation of other substrates such as ethane andpropane are possible. Due to its regular pore structure, the activity ofthe MOF catalyst is not reduced by fixation. It may even introduce anadditional positive aspect as suggested by the higher TON of the MOFcatalyst over the homogeneous ones. The pore sizes and shapes of MOFscan act as a reaction vessel with tunable size and polarity. This canenhance selectivity and increase affinity for a particular substrate.This tunability can be employed to target a specific product as shown bycomparison of MOF-V150 and MIL-47. Furthermore, MOFs provide a highdensity of accessible active sites. However, it should be kept in mindthat crystal defects might create open vanadium metal sites which couldbe responsible for the catalytic activity.

Results for ethane oxidative reaction:

TABLE 3 Product yields for MOF-V150, MIL- 47, and VOSO₄ in the absenceof CO Propanoic Acetic ^([a])Catalysts/ acid acid Trifluoroethyl TotalYield (%) (P.A)^([b]) (AcOH)^([c]) acetate (TM)^([d]) yield^([e])MOF-V150 4 43 14 61 MIL-47 3 41 25 69 VOSO₄ 1 36 0 37 ^([a])Reactionconditions: At ambient temperature, 10 bars of C₂H₆ pressure wasintroduced to a mixture containing, a MOF catalyst, K₂S₂O₈ (4 mmol), andTFA (7.5 ml). The mixture was then heated at 80° C. for 20 hrs.^([b])P.A yield was calculate as [C₂H₅CO₂H])/[K₂S₂O₈]. ^([c])AcOH yieldwas calculate as [CH₃CO₂H])/[K₂S₂O₈]. ^([d])TM yield was calculated as([CF₃CO₂CH₃]/[K₂S₂O₈]). ^([e])Total yield was calculated as{[C₂H₅CO₂H] + [CH₃CO₂H]) + [CF₃CO₂CH₃])/[K₂S₂O₈]} (excluding gaseousproduct).

Results for ethane oxidative carbonylation reaction:

TABLE 4 Product yields for MOF-V150, MIL-47, and VOSO₄ in the presenceof CO Propanoic Acetic Catalysts/Yield acid acid Trifluoroethyl Total(%)^([a]) (P.A)^([b]) (AcOH)^([c]) acetate (TM)^([d]) yield^([e])MOF-V150 32 25 22 80 MIL-47 63 14 3 78 VOSO₄ 62 10 0.5 72 ^([a])Reactionconditions: At ambient temperature, 10 bars of C₂H₆ pressure (25° C.)and 10 bars of CO pressure were introduced to a mixture containing, aMOF catalyst, K₂S₂O₈ (4 mmol), and TFA (7.5 ml). The mixture was thenheated at 80° C. for 20 hrs. ^([b])P.A yield was calculate as[C₂H₅CO₂H])/[K₂S₂O₈]. ^([c])AcOH yield was calculate as[CH₃CO₂H])/[K₂S₂O₈]. ^([d])TM yield was calculated as([CF₃CO₂CH₃]/[K₂S₂O₈]). ^([e])Total yield was calculated as{[C₂H₅CO₂H] + [CH₃CO₂H]) + [CF₃CO₂CH₃])/[K₂S₂O₈]} (excluding gaseousproduct).

TABLE 5 Total ester selectivity for MOFs in the presence of CO Ave esterselectivity Catalysts (%) * MOF-V150 69 MIL-47 60 * TM selectivity wascalculated as molar ratio of AcOH to total molar of products excludinggaseous product.

TABLE 6 Effect of pores on product distribution in the presence of COLess open More open MIL-47 pores pores Ethyl acetate yield (ave %) 0 17Trifluoroethyl acetate yield (ave %) 28 35 Ester selectivity (ave %) 6081 Total yield (ave %) 66 79

This disclosure describes the synthesis and use of vanadium containingframeworks for oxidizing and functionalizing alkanes. Although, MOFswith vanadium as part of the SBU are useful, post-synthesis metallatedmaterials can also be used.

A number of embodiments of the invention have been described.Nevertheless, it will be understood that various modifications may bemade without departing from the spirit and scope of the invention.Accordingly, other embodiments are within the scope of the followingclaims.

What is claimed is:
 1. A method to convert an alkane to an alcohol orcarboxylic acid by contacting the alkane with a catalytically activeheterogeneous vanadium containing metal organic framework (MOF) in thepresence of an oxidant, wherein the vanadium containing MOF comprises aplurality of repeating cores comprising vanadium or vanadium ion(s) thatare linked together by organic linking moieties.
 2. The method of claim1, wherein the alkane is a linear (C₁-C₁₂)alkane.
 3. The method of claim1, wherein the method is carried out in the presence of CO.
 4. Themethod of claim 1, wherein the oxidant is K₂S₂O₈.
 5. The method of claim1, wherein the alkane is converted to a carboxylic acid.
 6. The methodof claim 1, wherein the vanadium ion(s) is selected from the groupconsisting of V⁵⁺, V⁴⁺, V³⁺, and V²⁺.
 7. The method of claim 1, whereinthe metal organic framework comprises vanadium or vanadium ions withoctahedral coordination spheres.
 8. The method of claim 1, wherein themetal organic framework has a linking moiety with a parent chainselected from the group consisting of hydrocarbon, hetero-alkane,hetero-alkene, hetero-alkyne, and heterocycle; and wherein the parentchain is functionalized with at least one linking cluster.
 9. The methodof claim 1, wherein the metal organic framework is generated from aplurality of linking moieties comprising one or more of structuralFormulae I, II, III, IV, V, VI, VII, VIII, IX and X:

wherein: R¹-R⁴, R¹⁶-R²⁰, R²³-R³⁰, R³⁸-R⁹⁶ are independently selectedfrom the group consisting of H, functional group (FG), (C₁-C₂₀)alkyl,substituted (C₁-C₂₀)alkenyl, substituted (C₁-C₂₀)alkenyl,(C₁-C₂₀)alkynyl, substituted (C₁-C₂₀)alkynyl, hetero-(C₁-C₂₀)alkyl,substituted hetero-(C₁-C₂₀)alkyl, hetero-(C₁-C₂₀)alkenyl, substitutedhetero-(C₁-C₂₀)alkenyl, hetero-(C₁-C₂₀)alkynyl, substitutedhetero-(C₁-C₂₀)alkynyl, (C₁-C₂₀)cycloalkyl, substituted(C₁-C₂₀)cycloalkyl, aryl, substituted aryl, heterocycle, substitutedheterocycle, —C(R⁵)₃, —CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶,—OC(R⁵)₃, —OCH(R⁵)₂, —OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶, and

 wherein R¹ and R³ may be linked together to form a substituted orunsubstituted ring selected from the group consisting of cycloalkyl,aryl and heterocycle, wherein R² and R⁴ may be linked together to form asubstituted or unsubstituted ring selected from the group consisting ofcycloalkyl, aryl and heterocycle, wherein R¹⁸ and R¹⁹ may be linkedtogether to form a substituted or unsubstituted ring selected from thegroup consisting of cycloalkyl, aryl and heterocycle, wherein R²⁴ andR²⁵ may be linked together to form a substituted or unsubstituted ringselected from the group consisting of cycloalkyl, aryl and heterocycle,and/or wherein R²⁸ and R²⁹ may be linked together to form a substitutedor unsubstituted ring selected from the group consisting of cycloalkyl,aryl and heterocycle; R⁵ is selected from the group consisting of FG,(C₁-C₂₀)alkyl, (C₁-C₂₀)substituted alkyl, (C₁-C₂₀)alkenyl, substituted(C₁-C₂₀)alkenyl, (C₁-C₂₀)alkynyl, substituted (C₁-C₂₀)alkynyl,hetero-(C₁-C₂₀)alkyl, substituted hetero-(C₁-C₂₀)alkyl,hetero-(C₁-C₂₀)alkenyl, substituted hetero-(C₁-C₂₀)alkenyl,hetero-(C₁-C₂₀)alkynyl, substituted hetero-(C₁-C₂₀)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester; R₆ is one or more substitutedor unsubstituted rings selected from the group consisting of cycloalkyl,aryl, and heterocycle; Z is either a C or N; and X is a number from 0 to10.
 10. The method of claim 1, wherein the metal organic framework isgenerated from a plurality of linking moieties comprising structuralFormula I, II, III, IV, V, VI, VII, VIII, IX or X:

wherein: R¹-R⁴, R¹⁵-R²⁰, R²³-R³⁰, R³⁸-R⁹⁶ are independently selectedfrom the group consisting of H, functional group (FG), (C₁-C₂₀)alkyl,substituted (C₁-C₂₀)alkyl, (C₁-C₂₀)alkenyl, substituted (C₁-C₂₀)alkenyl,(C₁-C₂₀)alkynyl, substituted (C₁-C₂₀)alkynyl, hetero-(C₁-C₂₀)alkyl,substituted hetero-(C₁-C₂₀)alkyl, hetero-(C₁-C₂₀)alkenyl, substitutedhetero-(C₁-C₂₀)alkenyl, hetero-(C₁-C₂₀)alkynyl, substitutedhetero-(C₁-C₂₀)alkynyl, (C₁-C₂₀)cycloalkyl, substituted(C₁-C₂₀)cycloalkyl, aryl, substituted aryl, heterocycle, substitutedheterocycle, —C(R⁵)₃, —CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶,—OC(R⁵)₃, —OCH(R⁵)₂, —OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶, and

 wherein R¹ and R³ may be linked together to form a substituted orunsubstituted ring selected from the group consisting of cycloalkyl,aryl and heterocycle, wherein R² and R⁴ may be linked together to form asubstituted or unsubstituted ring selected from the group consisting ofcycloalkyl, aryl and heterocycle, wherein R¹⁸ and R¹⁹ may be linkedtogether to form a substituted or unsubstituted ring selected from thegroup consisting of cycloalkyl, aryl and heterocycle, wherein R²⁴ andR²⁵ may be linked together to form a substituted or unsubstituted ringselected from the group consisting of cycloalkyl, aryl and heterocycle,and/or wherein R²⁸ and R²⁹ may be linked together to form a substitutedor unsubstituted ring selected from the group consisting of cycloalkyl,aryl and heterocycle; R⁵ is selected from the group consisting of FG,(C₁-C₂₀)alkyl, (C₁-C₂₀)substituted alkyl, (C₁-C₂₀)alkenyl, substituted(C₁-C₂₀)alkenyl, (C₁-C₂₀)alkynyl, substituted (C₁-C₂₀)alkynyl,hetero-(C₁-C₂₀)alkyl, substituted hetero-(C₁-C₂₀)alkyl,hetero-(C₁-C₂₀)alkenyl, substituted hetero-(C₁-C₂₀)alkenyl,hetero-(C₁-C₂₀)alkynyl, substituted hetero-(C₁-C₂₀)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester; R⁶ is one or more substitutedor unsubstituted rings selected from the group consisting of cycloalkyl,aryl, and heterocycle; Z is either a C or N; and X is a number from 0 to10.
 11. The method of claim 1, wherein the metal organic framework isgenerated from a plurality of linking moieties comprising one or more ofstructural Formulae I, II, III, IV, V, VI, VII, and VIII:

wherein: R¹-R⁴, R¹⁵-R²⁰, R²³-R³⁰, R³⁸-R⁸⁸ are independently selectedfrom the group consisting of H, functional group (FG), (C₁-C₆)alkyl,substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted (C₁-C₆)alkenyl,(C₁-C₆)alkynyl, substituted (C₁-C₆)alkynyl, hetero-(C₁-C₆)alkyl,substituted hetero-(C₁-C₆)alkyl, hetero-(C₁-C₆)alkenyl, substitutedhetero-(C₁-C₆)alkenyl, hetero-(C₁-C₆)alkynyl, substitutedhetero-(C₁-C₆)alkynyl, (C₁-C₆)cycloalkyl, substituted (C₁-C₆)cycloalkyl,aryl, substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶, and

 wherein R¹ and R³ may be linked together to form a substituted orunsubstituted ring selected from the group consisting of cycloalkyl,aryl and heterocycle, wherein R² and R⁴ may be linked together to form asubstituted or unsubstituted ring selected from the group consisting ofcycloalkyl, aryl and heterocycle, wherein R¹⁸ and R¹⁶ may be linkedtogether to form a substituted or unsubstituted ring selected from thegroup consisting of cycloalkyl, aryl and heterocycle, wherein R²⁴ andR²⁵ may be linked together to form a substituted or unsubstituted ringselected from the group consisting of cycloalkyl, aryl and heterocycle,and/or wherein R²⁸ and R²⁹ may be linked together to form a substitutedor unsubstituted ring selected from the group consisting of cycloalkyl,aryl and heterocycle; R⁵ is selected from the group consisting of FG,(C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl, substituted(C₁-C₆)alkenyl, (C₁-C₆)alkynyl, substituted (C₁-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₁-C₆)alkenyl,hetero-(C₁-C₆)alkynyl, substituted hetero-(C₁-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester; R₆ is one or more substitutedor unsubstituted rings selected from the group consisting of cycloalkyl,aryl, and heterocycle; and X is a number from 0 to
 3. 12. The method ofclaim 1, wherein the metal organic framework is generated from aplurality of linking moieties comprising one or more of structuralFormulae I, II, III, IV, V, VI, VII, and VIII:

wherein: R¹-R⁴, R¹⁵-R²⁰, R²³-R³⁰, R³⁸-R⁸⁸ are independently selectedfrom the group consisting of H, functional group (FG), (C₁-C₆)alkyl,substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted (C₁-C₆)alkenyl,(C₁-C₆)alkynyl, substituted (C₁-C₆)alkynyl, hetero-(C₁-C₆)alkyl,substituted hetero-(C₁-C₆)alkyl, hetero-(C₁-C₆)alkenyl, substitutedhetero-(C₁-C₆)alkenyl, hetero-(C₁-C₆)alkynyl, substitutedhetero-(C₁-C₆)alkynyl, (C₁-C₆)cycloalkyl, substituted (C₁-C₆)cycloalkyl,aryl, substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶, and

 wherein R¹ and R³ may be linked together to form a substituted orunsubstituted ring selected from the group consisting of cycloalkyl,aryl and heterocycle, wherein R² and R⁴ may be linked together to form asubstituted or unsubstituted ring selected from the group consisting ofcycloalkyl, aryl and heterocycle, wherein R¹⁸ and R¹⁹ may be linkedtogether to form a substituted or unsubstituted ring selected from thegroup consisting of cycloalkyl, aryl and heterocycle, wherein R²⁴ andR²⁵ may be linked together to form a substituted or unsubstituted ringselected from the group consisting of cycloalkyl, aryl and heterocycle,and/or wherein R²⁸ and R²⁹ may be linked together to form a substitutedor unsubstituted ring selected from the group consisting of cycloalkyl,aryl and heterocycle; R⁵ is selected from the group consisting of FG,(C₁-C₆)alkyl, (C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl, substituted(C₁-C₆)alkenyl, (C₁-C₆)alkynyl, substituted (C₁-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₁-C₆)alkenyl,hetero-(C₁-C₆)alkynyl, substituted hetero-(C₁-C₆)alkynyl, hemiacetal,hemiketal, acetal, ketal, and orthoester; R₆ is one or more substitutedor unsubstituted rings selected from the group consisting of cycloalkyl,aryl, and heterocycle; and X is a number from 0 to
 3. 13. The method ofclaim 1, wherein the metal organic framework is generated from a linkingmoiety comprising structural Formula I:

wherein: R¹-R⁴ are independently selected from the group consisting ofH, halo, amine, cyano, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄,AsO₃H, AsO₄H, P(SH)₃, As(SH)₃, CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃,Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₄, POSH, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃,(C₁-C₆)alkyl, substituted (C₁-C₆)alkyl, (C₁-C₆)alkenyl, substituted(C₂-C₆)alkenyl, (C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl,hetero-(C₁-C₆)alkyl, substituted hetero-(C₁-C₆)alkyl,hetero-(C₁-C₆)alkenyl, substituted hetero-(C₂-C₆)alkenyl,hetero-(C₂-C₆)alkynyl, substituted hetero-(C₂-C₆)alkynyl, aryl,substituted aryl, heterocycle, substituted heterocycle, —C(R⁵)₃,—CH(R⁵)₂, —CH₂R⁵, —C(R⁶)₃, —CH(R⁶)₂, —CH₂R⁶, —OC(R⁵)₃, —OCH(R⁵)₂,—OCH₂R⁵, —OC(R⁶)₃, —OCH(R⁶)₂, —OCH₂R⁶,

 wherein R¹ and R³ may be linked together to form a substituted orunsubstituted ring selected from the group consisting of cycloalkyl,aryl and heterocycle, and/or wherein R² and R⁴ may be linked together toform a substituted or unsubstituted ring selected from the groupconsisting of cycloalkyl, aryl and heterocycle; R⁵ is selected from thegroup comprising hydroxyl, amine, thiol, cyano, carboxyl, (C₁-C₆)alkyl,(C₁-C₆)substituted alkyl, (C₁-C₆)alkenyl, substituted (C₂-C₆)alkenyl,(C₂-C₆)alkynyl, substituted (C₂-C₆)alkynyl, hetero-(C₁-C₆)alkyl,substituted hetero-(C₁-C₆)alkyl, hetero-(C₁-C₆)alkenyl, substitutedhetero-(C₂-C₆)alkenyl, hetero-(C₂-C₆)alkynyl, substitutedhetero-(C₂-C₆)alkynyl, hemiacetal, hemiketal, acetal, ketal, andorthoester; R⁶ is one or more substituted or unsubstituted ringsselected from the group consisting of cycloalkyl, aryl, and heterocycle;and X is a number from 0 to
 3. 14. The method of claim 13, wherein thelinking moiety is selected from the group consisting of


15. The method of claim 1, wherein at least one of the functional groupsof the metal organic framework is further modified, substituted, oreliminated with a different functional group post-synthesis of theframework.
 16. The method of claim 15, wherein the metal organicframework is further modified by adding a functional group postsynthesis of the framework that has one or more properties selected fromthe group consisting of: binds a metal ion, increases the hydrophobicityof the framework, modifies the gas sorption of the framework, modifiesthe pore size of the framework, and tethers a catalyst to the framework.17. The method of claim 1, wherein the metal organic framework comprises[V(O)(C₁₀H₈O₄)] or [V(O)(C₈H₄O₄)].
 18. The method of claim 1, whereinthe alkane is either methane or ethane.
 19. The method of claim 1,wherein the method converts methane to acetic acid with up to a 70%yield.
 20. The method of claim 1, wherein the method can be performedmultiple times with the same MOF.